SK279651B6 - Zeolite- and/or layered silicate-activated detergent composition - Google Patents

Abstract

Disclosed is a built detergent composition, comprising one or more anionic, nonionic or cationic detersive surfactants, or mixtures thereof, optional detersive adjuncts, and optional auxiliary builders, wherein the composition contains at least about 1 percent by weight of a zeolite or layered silicate builder, or mixture thereof; and at least about 1 percent by weight of a polyhydroxy fatty acid amide material of formula (I) wherein: R1 is H, C1-C4 alkyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof; R2 is a C5-C31 hydrocarbyl; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.

Description

The invention relates to detergent compositions in which detergent builders are combined with a zeolite or layered silicate base (i.e., layered silicate), or mixtures thereof, with polyhydroxy fatty acid amides.

BACKGROUND OF THE INVENTION

Various builders have been proposed for use in detergent compositions. Such materials serve a variety of functions, including hardness suppression, peptization, pH control, and the like. Tripolyphosphate has been a selected activator for many years, but recent developments in the art have brought about activating materials such as zeolites, various polycarboxylates, and the like. Currently, a number of fully formulated detergent compositions comprise a zeolite activator or a carboxylate activator, or mixtures thereof.

The development of high-performance phosphate-free laundry detergent compositions has been a major challenge for industry. In terms of effect, even the best zeolite activators often result in an underactivated situation in hard water. In addition, commercially available zeolite activating agents can cope with calcium hardness, but are not particularly effective against magnesium hardness. Recently, the possibility of using layered silicates as detergent activators has been discovered. Layered silicates, however, cope with magnesium hardness, but are somewhat less effective in controlling calcium hardness.

At present, almost all phosphate-free high performance granular detergents contain a zeolite activator component. Although zeolite-activated laundry detergents are widely marketed, the drawbacks are well known by the formulator. In order to increase the detergency performance of zeolite and layered silicate compositions, experienced formulators typically add a variety of detergent adjuvants to the detergent compositions. Thus, materials such as cleaning enzymes, soil release polymers, bleaches and bleach activators are used to increase the effectiveness of the activated detergent compositions.

In addition, it should also be noted that, although for several years new detergent formulators have sought to replace detergent-activated phosphates with equally effective phosphate-free detergents, there has recently been an interest to build detergents with reduced levels of oil-derived surfactants and other non-renewable sources.

A number of polyhydroxy fatty acid amides are further described in the art. For example, N-acyl, N-methyl glucamides are described by J.W. Goodby, M.A. Marcus, E. Chin, and P.L. Finn in The Thermotropic Liquid-Crystalline Properties of Some Straight Chain Carbohydrate Amphiphiles in Liquid Crystals, 1988, Vol. 3, no. 11, p. 1569-1581 and A. Muller-Fahmow, V. Zabel, M. Steif, and R. Hilgenfeld in Molecular and Crystal Structure of a Nonionic Detergent: Nonanoyl-N-methylglucamide in J. Chem. Soc. Chem. Commun., 1986, p. Recently, the use of N-alkyl polyhydroxyamide surfactants has been of particular interest for use in biochemistry, for example in the dissociation of biological membranes (see also, for example, the journal article N-D-Gluco).

-N-methyl-alkanamide Compounds and New Class chem. J., 1982, Vol. 207, p. 363-366, by J. E. K. Hildreth.

The use of N-alkyl glucamides in detergent compositions has also been discussed in the literature. U.S. Pat. No. 2,965,576, issued December 20, 1960; No. 809,060, published Feb. 18, 1959, discloses detergent compositions comprising anionic surfactants and certain amide surfactants, which may include N-methylglucamide added as a low temperature suds booster. These compounds include a straight chain N-acyl group of a straight chain of 10 to 14 carbon atoms. These compounds may also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfites and carbonates. It is also generally disclosed that additional ingredients may be included in the compositions for imparting desirable properties to the composition, such as fluorescent dyes, bleaching agents, fragrances, and the like.

U.S. Pat. No. 2,703,798, issued Aug. 8, 1955, refers to aqueous detergent compositions comprising the condensation reaction product of N-alkylglucamine and an aliphatic fatty acid ester. The product of this reaction is reported to be useful in aqueous detergent compositions without further purification. It is also known to prepare a sulfur ester of an acyl glucamine as described in U.S. Pat. No. 2,717,894, issued September 13, 1955.

PCT International Patent Application WO 83/04412, published Dec. 22, 1983 discloses amphiphilic compounds containing polyhydroxylaliphatic groups, designated as being useful for a variety of purposes, including use as a surfactant in cosmetics, pharmaceuticals, shampoos, lotions, eye ointments, emulsifiers and dosing agents in medicine and biochemistry to solubilize membranes, whole cells and other tissue samples, and to prepare liposomes. Included herein are compounds of formula R'CON (R) CH2R and RCON (R) R ', wherein R is hydrogen or an organic group, R ¹ is an aliphatic hydrocarbon group of at least three carbon atoms, and R is an aldose residue.

European patent specification no. No. 0 285 768, published Oct. 12, 1988, refers to the use of N-polyhydroxy fatty acid amides as thickeners in aqueous detergent systems. Included are amides of formula R 1 C (O) N (X) R 2, wherein R 1 is C 1 -C ₁₇ (preferably C 7 -C 17) alkyl, R ² is hydrogen, C 6 -C ¹⁸ (preferably C 1 -C 6) alkyl or alkene oxide and X is polyhydroxyalkyl having four to seven carbon atoms, e.g. Coconut fatty acid N-methylglucamide. The amide thickening properties are indicated to be particularly suitable for use in liquid paraffin sulfonate containing surfactant systems, although aqueous surfactant systems may contain other anionic surfactants such as alkylarylsulfonates, sulfosuccinic acid half ester salts and fatty alcohol ether sulfonates and nonionic surfactants. such as a polyglycol ether of a fatty alcohol, a polyglycol ester of a fatty acid, polypropylene oxide-polyethylene oxide blend polymers, etc. Examples are paraffin paraffin sulphonate / coconut fatty acid N-methylglucamide formulations / nonionic shampoo surfactant. In addition to the thickening properties, N-polyhydroxy fatty acid amides have been reported to have superior skin tolerance properties.

SK 279651Β6

U.S. Pat. No. 2,982,737, issued May 2, 1961, discloses urea-containing detergent bars, anionic sodium lauryl sulfate surfactant, and an N-alkylglucamide nonionic surfactant selected from N-methyl, N-sorbityl-lauramide and N methyl, N-sorbityl myristamide.

Other glucamide surfactants are described, for example, in German Pat. No. 2,226,872, published Dec. 20, 1972, which relates to a laundry composition comprising one or more surfactants and activating salts selected from polymeric phosphates, scavengers and scouring alkalis, improved by the addition of an N-acylpolyhydroxy-alkylamine of formula R1C ( O) N (R ₂ ) CH ₂ (CHOH) _n CH 2 OH wherein R 1 is C 1 -C 22 alkyl, R 2 is C 10 -C 22 alkyl and n is 3 or 4. N-acylpolyhydroxyalkylamine is added as an impurity suspending agent.

U.S. Pat. No. 3,654,166, issued April 4, 1972, discloses detergent compositions comprising at least one surfactant selected from the group of anionic zwitterionic surfactants and nonionic surfactants and fabric softeners, N-acyl, N- alkyl-polyhydroxyalkyl compounds of the formula R 1 N (Z) C (O) R 2 wherein R 1 is C ₀ -C ₂₂ alkyl, R 2 is C ₇ -C 2 alkyl, R 1 and R 2 have a total of 23 to 39 carbon atoms and Z is poly hydroxy alkyl can be _-CH2 (CHOH) _ln CH 2 OH, wherein m is 3 or 4.

U.S. Pat. 4,021,539 issued May 3, 1977 5 describes cosmetic compositions for treating the skin, comprising the N-polyhydroxyalkyl-amines which include compounds of formula RlNjRjCHjCHOHjmR ^2, R 1 _e j k d _e H, lower alkyl, hydroxy-lower alkyl, or aminoalkyl, as well as heterocyclic aminoalkyl, R is the same as R1, but both cannot be H and R2 is CH2OH or COOH.

French patent no. No. 1,360,018, issued Apr. 26, 1963, relates to formaldehyde solutions stabilized against polymerization by the addition of amides of formula RC (O) N (R 1) G, wherein R is a carboxyl functional group having at least seven carbon atoms, R 1 is hydrogen or a lower alkyl group; G is a glucitol group with at least 5 carbon atoms.

German patent specification no. 1261851 of 29 2, 1968, relates to glucamine derivatives useful as wetting and dispersing agents of the formula N (R) (R1) (R2) wherein R is a sugar residue of glucamine, Rl is a _C2-C1o The alkyl group and R 2 is C 1 -C 5 acyl group.

British patent no. No. 745,036, published February 15, 1956, relates to heterocyclic amides and their carboxylic esters, which are said to be useful as chemical mediators, emulsifiers, wetting and dispersing agents, fabric softeners, etc. The compounds are represented by the formula N (R) (R1) C (O) R2, wherein R is a residue of hexapentol or a carboxylic acid ester thereof, dehydrated, R1 is a monovalent hydrocarbon radical, and -C (O) R2 is an acyl radical of 2 up to 25 carbon atoms.

U.S. Pat. No. 3,312,627, issued April 4, 1967, discloses solid toilet blocks that are substantially devoid of anionic detergents and alkaline activating agents and which contain lithium soap of certain fatty acids, a surfactant selected from certain propolylene oxide-ethylenediamine-ethylene oxide condensates , propylene oxide-propylene glycol ethylene oxide condensates and polymerized ethylene glycol, and also contain a nonionic foaming component, which may include a polyhydroxyamide of the formula RC (O) (NR 1 R 2), wherein RC (O) contains from about 10 to about 14 carbon atoms, and R 1 and R 2 each have H or The C 1 -C 8 alkyl group comprises a total amount of carbon from about 2 to about 7 and a total number of hydroxyl substituent groups of from about 2 to about 6. A substantially similar solution is disclosed in U.S. Pat. 3 312 626, also issued April 4, 1967.

SUMMARY OF THE INVENTION

The invention is based on the discovery that some polyhydroxy fatty acid amide-containing detergent compositions can provide excellent overall cleaning performance with total or partial replacement of commonly used petroleum-derived surfactants such as linear alkyl benzene sulfonates. These polyhydroxy fatty acid amides can be obtained predominantly or wholly from natural renewable raw materials and, moreover, are degradable and have less aquatic toxicity. These polyhydroxy fatty acid amides can increase the solubility and dissolution of the surfactant and auxiliary activating salts during use of the detergent compositions. In addition, these polyhydroxy fatty acid amides can surprisingly enhance the effectiveness of zeolite-based and layered silicate activating ingredients under underactivated washing conditions.

The present invention provides a zeolite-activated detergent composition comprising one or more anionic, non-ionic or cationic detersive surfactants, or mixtures thereof, optionally detersive builders and optionally auxiliary builders, which according to the invention is characterized in that it contains at least 1 wt. % detergent activator of zeolite base or layered silicate or mixtures thereof and at least 1 wt. % of the amide material in the form of a polyhydroxy fatty acid amide of the formula

O Rl

II I

R ² - C-N- Z wherein R is H, C 1 -C 4 hydrocarbon group, 1,2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C 1 -C 4 alkyl, preferably C, or C 2 alkyl, most preferably C alkyl ( ie methyl), R 2 is a C 5 -C 31 hydrocarbon group preferably C 7 and C 9 alkyl, or straight chain alkenyl, more preferably C 9 -C 17 alkyl, or straight chain alkenyl, most preferably C 11 -C 17 alkyl, or straight chain alkenyl and Z is a linear hydrocarbon a group substituted by at least three hydroxyl groups directly attached to the hydrocarbon chain, or an alkoxylated derivative thereof, preferably ethoxylated or propoxylated.

In the detergent composition of the invention, the zeolite activator is preferably Zeolite A.

According to one embodiment of the invention, Z in the polyhydroxy fatty acid amide is derived from a reducing sugar, R1 is methyl and R2 is C9-C17 alkyl or alkenyl. For example, it contains -CH ₂ (CHOH) 4 CH ₂ OH.

Part Z in said polyhydroxy fatty acid amide may be derived from maltose. According to a preferred embodiment, the Z moiety in said polyhydroxy fatty acid amide is derived from a mixture of monosaccharides, disaccharides and possibly higher carbohydrates, wherein

The mixture comprises at least 1% of at least one disaccharide, preferably maltose.

The ratio of zeolite: polyhydroxy fatty acid amide in the detergent composition of the invention is from 1: 10 to 20: 1, preferably 1: 5 to 15: 1, most preferably 1: 3 to 10: 1.

The detergent composition of the invention may further comprise one or more anionic surfactants selected from the group consisting of alkyl sulfates, alkylethoxylated sulfates, alkyl ester sulfonates, preferably methyl ester sulfonates, alkyl benzene sulfonates. It may further comprise an alkyl ethoxylate or alkyl polyglycoside nonionic surfactant or a mixture thereof.

The detergent composition of the invention may also additionally contain a polycarboxylate activator.

Thus, the invention provides an improved cleaning surfactant system comprising zeolite and / or layered silicate based builders. According to the invention, polyhydroxy fatty acid amides are used in zeolite and / or layered silicate activated detergents to provide enhanced detergency.

The individual components of the detergent compositions of the invention will now be described first. First, polyhydroxy fatty acid amide surfactants will be described in more detail.

The compositions of the invention will contain at least about 1%, and typically from about 3% to about 50%, and preferably from about 3% to about 30%, of the disclosed polyhydroxy fatty acid amide surfactant.

The amide surfactant component of the present invention based on polyhydroxy fatty acid amide has the structural formula:

O R1

II I

R2-C-N-Z, (I) wherein R ¹ is H, C 1 -C 4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C 1 -C 4 alkyl, preferably C, or C 2 alkyl, most preferably C alkyl (ie methyl) and R ² is a C 5 -C 31 hydrocarbon group, preferably a straight chain C 7 -C 19 alkyl or alkenyl, more preferably a straight chain C 9 -C 17 alkyl or alkenyl, and most preferably a straight chain C 1 -C 17 alkyl or alkenyl or a mixture thereof; and Z is a linear hydrocarbon group substituted with at least 3 hydroxyl groups directly attached to the hydrocarbon chain, or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof. Part Z will preferably be derived from a reducing sugar in a reductive amination reaction; more preferably Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, galactose, mannose, and xylose. As raw materials, high dextrose cereal syrup, high maltose cereal syrup, as well as the individual sugars mentioned may be used. These cereal syrups may provide a mixture of sugar components for Z. However, it should be noted that in no case is the exclusion of other suitable raw materials monitored. Z preferably will be selected from the group consisting of

CH 2 - (CHOH) _n -CH ₂ OH, -CH (CH 2 OH) - (CHOH) _n . 1 -CH ₂ OH,

-CH 2 - (CHOH) 2 (CHOR ') (CHOH) -CH ₂ OH and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5 inclusive, R' is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, especially -CH 2 - (CHOH) 4 -CH ₂ OH.

In formula (I), R 1 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, Ν-2-hydroxyethyl or N-2-hydroxypropyl.

R 2 -CO-N <can be, for example, coconut fatty acid amide, stearamide, oleamide, lauramide, caprinamide, palmitamide, tallow amide, etc.

Z may be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, N-1-deoxygalactityl, N-1-deoxymannityl, 1-deoxymaltotriotityl, etc.

Methods for making polyhydroxy fatty acid amides are known in the art. In general, they can be produced by reacting an alkylamine with a reducing sugar and a reductive amination reaction to form the corresponding N-alkyl-polyhydroxyamine and then reacting the N-alkyl-polyhydroxyamine with a fatty aliphatic ester or triglyceride in the condensation / amination process to form the amide N-alkyl product. , N-polyhydroxy fatty acid. Processes for making compositions containing polyhydroxy fatty acid amides are described, for example, in United Kingdom patent no. No. 809,060, published Feb. 18, 1959, U.S. Pat. No. 2,965,576, issued Dec. 20, 1960, U.S. Pat. No. 2,703,798, issued Mar. 8, 1955, and U.S. Pat. No. 4,198,424, issued Dec. 25, 1934, the disclosure of which is incorporated herein by reference.

In one method of making N-alkyl or N-hydroxyalkyl, N-deoxyglycityl fatty acid amides, wherein the glycityl component is derived from glucose and the N-alkyl or N-hydroxyalkyl functionality is N-methyl, N-ethyl, N-propyl, N -butyl, N-hydroxyethyl or N-hydroxypropyl, the product is obtained by reacting an N-alkyl or N-hydroxyalkyl glucamine with a fatty ester selected from fatty methyl esters, fatty ethyl esters and fatty triglycerides in the presence of a catalyst selected from the group consisting of tritium phosphate, trisodium phosphate , tripotassium phosphate, tetrasodium pyrophosphate, pentasodium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, disodium tartrate, potassium potassium tartrate, trisodium tartrate, trisodium tartrate, sodium, inc potassium silicates, basic sodium aluminosilicates and basic potassium aluminosilicates, and mixtures thereof. The amount of catalyst is preferably from 0.5 mol% to about 50 mol%, more preferably from about 2.0 mol% to about 10 mol%, based on the N-alkyl- or N-hydroxyalkyl-glucamine molar base. The reaction is preferably carried out at a temperature of from about 138 ° C to about 170 ° C for typically from about 20 to about 90 minutes. When carbohydrates are used as a fatty ester source in the reaction mixture, the reaction is also preferably carried out using from about 1 to about 10 wt. % of a phase transfer agent calculated on the basis of the weight percent of the total reaction mixture selected from fatty alcohol polyethoxylates, alkyl polyglycosides, a linear glycamide surfactant and mixtures thereof.

SK 279651Β6

Preferably, this procedure is carried out as follows. First, the fatty ester is preheated to a temperature of from about 138 ° C to about 170 ° C. Then, N-alkyl or N-hydroxyalkyl-glucamine is added to the heated fatty acid ester and mixed to the extent necessary to form a biphasic liquid / liquid mixture. The catalyst is then mixed into the reaction mixture and stirred for the indicated reaction time.

Also preferably, from about 2% to about 20% of the preformed amide product N-alkyl / N-hydroxy alkyl, N-linear glucosyl fatty acid, based on the weight of the reactants, is added to the reaction mixture as a phase transfer agent when the fatty ester is triglyceride. This also vaccinates the reaction, thereby increasing the reaction rate. A detailed experimental procedure is given.

The amide materials in the form of polyhydroxy fatty acid amides also used herein provide advantages for the detergent formulator in that they can be prepared wholly or primarily from natural, renewable starting materials and that they are degradable. They are also characterized by low aquatic life toxicity.

It will be appreciated that, together with the polyhydroxy fatty acid amides of formula (I), the processes for their production also typically produce a number of nonvolatile by-products such as esteramides and cyclic polyhydroxy fatty acid amide. The level of these by-products will vary depending on the particular reagents and process conditions. Preferably, the polyhydroxy fatty acid amide included in the detergent compositions of the invention will be used in such a form that the composition comprising the polyhydroxy fatty acid amide added to the detergent comprises less than 10% and preferably less than 4% cyclic polyhydroxy fatty acid amide. The preferred processes described are advantageous in that they yield relatively low by-product yields, including such cyclic amide by-products.

Activating additives based on zeolite and layered silicate will now be described. The compositions may comprise an activator of zeolite or layered silicate, or a mixture thereof.

The level of the activating additive of zeolite and / or layered silicate may vary widely, depending on the end use of the composition and its desired physical form. The detergent compositions will contain at least about 1% of such an activating additive. Liquid formulations typically comprise from about 5% to about 50%, more typically from about 5% to about 30%, by weight of the activating additive. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50%, by weight of the activating additive. However, lower or higher levels of activating ingredients are not excluded. Preferably, the weight ratio of the activating additive of zeolite or layered silicate, or a mixture thereof, to the polyhydroxy fatty acid amide is from about 1:10 to about 20: 1, more preferably from about 1: 5 to about 15: 1, most preferably from about 1: 1. : 2 to about 10: 1.

Zeolite builders are categories of aluminosilicate builders which have gained prominence in the composition of current high performance detergents, especially granular formulations. The zeolite builders of the composition of the invention may have a crystalline or amorphous structure and may occur naturally or may be derived synthetically. Methods for producing zeolite materials are well known in the art, see e.g. U.S. Pat. No. 4,985,669, issued Oct. 12, 1976, which is incorporated herein by reference. Preferred synthetic ion exchange zeolite materials useful in the present case are available under the designations Zeolite A, Zeolite P (B) and Zeolite X. Generally, zeolite builders of the composition of the invention include those having the formula:

Na _z [(A10 ₂ ) _z (SiO ₂ ) y] .xH ₂ O, wherein z and y are integers of at least 6, wherein the molar ratio of the club from 1 to about 0.5 and x is an integer from about 15 to about 264, and the material has a magnesium ion exchange capacity of at least 50 milligrams equivalents of CaCCfy hardness per gram of anhydrous aluminosilicate. In a particularly preferred embodiment, the crystalline ion exchange silicate material has the formula:

Nai 2 [(AlO ₂ ) 12 (SiO 2) 12] xH ₂ O, where x is from about 20 to about 30, especially about 27. This material is known as Zeolite A.

Layer silicate based activating agents are also known in the art - see, for example, sodium silicate layered activating agents described in U.S. Pat. No. 4,664,839, issued Jan. 12,1987, which is incorporated herein by reference.

Preferably, detergents for use below these temperatures are below about 50 ° C, in particular below about 40 ° C, are substantially free of borate-containing activating agents and borate-forming activating agents. In this context, substantially free of borate-containing activators and borate-forming activators means that the composition comprises no more than about 2 wt. % of a borate-containing activator or a borate-forming activator and preferably no more than 1%, more preferably about 0.5%, and most preferably substantially 0%.

In addition to the polyhydroxy fatty acid amides and zeolite activating additive, the compositions of the invention comprise one or more other surfactants, which may be anionic, cationic or nonionic. Typically, the surfactant system will include one or more anionic and / or nonionic surfactants optionally used to the polyhydroxy fatty acid amide. It is particularly preferred to include an anionic surfactant for effective overall cleaning under a wide variety of washing conditions. The advantages of the invention are particularly evident when its compositions contain hardness-sensitive surfactants such as alkylsulfonates, alkylsulfonates (e.g., methylsulfonate), alkylalkoxylated sulfonates (e.g., alkylethoxylated sulfonates), and alkylbenzenesulfonates (e.g., linear alkylbenzenesulfonate). It is further desirable to further incorporate a conventional nonionic surfactant such as an alkyl ethoxylate or an alkyl glycoside as described. Typically, the amount of additional detersive surfactant present is from about 1% to about 50% by weight of the detergent composition, preferably from about 3% to about 40%, more preferably from about 5% to about 30%. Suitable surfactants will be described.

The first group are alkyl ester sulfonate surfactants. These surfactants include linear carboxylic acid esters of C3-C20 (i.e. fatty acids) that are sulfonated with SO3 gas according to The Joumal of the American Oil Chemists

Society, 52 (1975), p. 323 - 329. Suitable starting

Materials include natural fatty substances such as tallow, palm oil, coconut oil, etc.

Preferred alkyl ester sulfonate surfactants, especially for washing, comprise alkyl ester sulfonate surfactants of the structural formula:

ABOUT

II

R3 —CH — C — OR4,

Even with ₃ M where R ³ is a C 8 -C 20 hydrocarbyl, preferably an alkyl, or combination thereof, R ⁴ is C; The -Cfi hydrocarbon group, preferably alkyl, or a combination thereof, and M is a cation which forms a water-soluble salt with an alkyl ester sulfonate. Suitable salts include metal salts such as sodium, potassium and lithium salts and substituted or unsubstituted ammonium or ammonium salts such as methyl, dimethyl, trimethyl and quaternary ammonium ions, for example tetramethyl ammonium and dimethyl piperidinium and cations derived from alkanoamines, e.g. monoethanolamine, dietamolamine and triethanolamine. Preferably, R 3 C [4-C | (5 alkyl and R ⁴ is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein ^R3 is C14-C16 alkyl.

The alkylsulfonate surfactants used in the compositions of the invention are water-soluble salts or acids of the formula ROSO 3 M, wherein R is preferably C 1 -C 18 hydrocarbyl, preferably alkyl or hydroxyalkyl having a C 1 -C 20 alkyl component, more preferably C 12 -C 18 alkyl or hydroxyalkyl and M is H or a cation, e.g. an alkali metal cation (e.g., sodium, potassium and lithium), substituted or unsubstituted ammonium cations such as methyl, dimethyl and trimethylammonium and dimethylpiperidinium, and alkanolamine derived cations such as ethanolamine, diethanolamine, triethanolamine and mixtures thereof. Typically, C12-C16 alkyl chains are preferred for lower wash temperatures (e.g., below 50 ° C) and C 16 -C 18 alkyl chains are preferred at higher wash temperatures (e.g., above about 50 ° C).

The alkylalkoxylated sulfate surfactants used in the compositions of the invention are water-soluble salts or acids of formula RO (A) _m . SO3M, wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably a C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy group, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and 3, and M is H or a cation, which may be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfonates are contemplated herein. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium, and quaternary ammonium ions such as tetramethylammonium and dimethylpiperidinium, and alkanolamine-derived cations, e.g. monoethanolamine, diethanolamine and triethanolamine and mixtures thereof. Exemplary surfactants are C 12 -C 18 alkyl polyethoxylate (1,0) sulfate, C 12 -C 18 alkyl polyethoxylate (2,25) sulfate, C 12 -C 18 alkyl polyethoxylate (3,0) sulfate, and C 12 -C 18 alkyl polyethoxylate (4.0) ) sulfate, where M is usually selected from sodium and potassium.

Other anionic surfactants useful for cleaning purposes may also be included in the detergent compositions of the invention. These may include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-, and triethanolamine salts) of the soap, C9-C20 linear alkylbenzene sulfonates, C8-C22, and secondary alkanesulfonates, C8-C24ole sulfonic acid, sulfonated polysulfonates sulfonating the pyrolized alkaline earth metal citrate product, for example, as described in British Patent Specification No. 5,938,549; 1 082 179, alkylglycerol sulfonates, fatty acylglycerol sulfonates, oleyl glycerosulfate fatty acids, alkylphenolethylene oxide ether sulfates, paraffin sulfates, alkyl phosphates, isethionates such as N-acylisethionates, acyltaurates, fatty acid amides or methyllauride, and succinosulfate monosuccinates; (18 monoesters), sulfosuccinate diesters (especially saturated C12-C18 monoesters) sulfosuccinate diesters (especially saturated and unsaturated C5-C14 diesters), N-acyl sarcosinates, alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates, non-ionic unsolvated compounds and alkyl polyethoxycarboxylates as compounds of the formula:

RO (CH 2 CH 2 O) k CH 2 COO-M ⁺ , wherein R is C 8 -C 22 alkyl, k is an integer from 0 to 10 and M is a cation forming a soluble salt and fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and resin acids and hydrogenated resin acids present in or derived therefrom. Further examples are described in Surface Active Agents and Detergents (Vol. I and II by Schwartz, Perry and Berch). A number of such surfactants are also generally described in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975, ed. 23, r. 58 to stí. 29, r. 23, which is incorporated herein by reference.

Suitable nonionic surfactants are generally described in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975, et al. 13, r. 14 to stí. 16, r. 6, which is incorporated herein by reference. Exemplary but not limiting classes of suitable nonionic surfactants are disclosed.

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols. In general, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkylphenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched configuration with alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from 5 to about 25 moles of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include IgepalTM CO-630, available from GAF Corporation and TritonTM X-45, X-114, X-100 and X-102, all available from the Rohm and Haas Company. These surfactants are commonly referred to as alkylphenolalkoxylates, e.g. alkyl phenol ethoxylates.

2. The condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and typically contains from about 10 to about 20 carbon atoms. Particularly preferred are condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with

Wheel 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include TergitolTM 15-S-9 (condensation product of C uC 15 linear secondary alcohol with 9 moles of ethylene oxide), TergitolTM 24-L-6 NMW (condensation product of C12-C14 primary alcohol with 6 moles) ethylene oxide with narrow molecular weight distribution), supplied by both Union Carbide Corporatin, Neodol ™ 45-9 (condensation product C14-C15) linear alcohol with 9 moles of ethylene oxide), Neodol ™ 23-6.5 (condensation product C12-C13 linear alcohol with 6.5 moles ethylene oxide) NeodolTM 45.7 (condensation product of C14-C15) linear alcohol with 7 moles of ethylene oxide), NeodolTM 45.4 (condensation product of C14-C15 linear alcohol with 4 moles of ethylene oxide) supplied by Company and KyroTM poB (condensation C13-C15) of alcohol with 9 moles of ethylene oxide) supplied by Procter and Gambia Co. These surfactants are commonly referred to as alkyl ethoxylate.

3. The condensation products of ethylene oxide with a hydrophobic base, formed by the condensation of propolyene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a relative molecular weight of from about 1500 to about 1800 and is insoluble in water. The addition of polyoxyethylene moieties to this hydrophobic moiety tends to increase the solubility of the molecule as a whole in water and the liquid nature of the article is maintained until the polyoxyethylene content is about 50% of the total weight of the condensation product, corresponding to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially available Pluronic ™ surfactants available from BASF.

4. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic portion of these products consists of a reaction product of ethylenediamine and excess propylene oxide and generally has a relative molecular weight of from about 2500 to about 3000. This hydrophobic portion is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a relative molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain commercially available Tetronic ™ compounds available from BASF.

5. Semi-polar nonionic surfactants are special categories which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and 1 to 3 hydroxyalkyl groups carbon atoms; furthermore, water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups of from 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.

Semi-polar nonionic detergent surfactants include amine oxide surfactants of the formula:

ABOUT

I

R 3 (OR 4) _x N (R 5) _2; wherein R3 is an alkyl, hydroxyalkyl or alkylphenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof, x is from 0 to 31 and each R ⁵ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 into about 3 ethylene oxide groups. The R 5 moieties may be attached to each other, for example, through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants include, in particular, C 10 -C 18 alkyl dimethylammonium oxides and C 8 -C 12 alkoxyethyldihydroxyethylamine oxides.

6. Alkylpolysaccharides disclosed in U.S. Pat. No. 4,565,647, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, e.g. polyglycoside, a hydrophilic group comprising from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 carbohydrate units. Any reducing saccharide containing 5 or 66 carbon atoms may be used, for example glucose, galactose, and galactosyl moieties may be substituted for the glucosyl moiety (optionally, the hydrophobic moiety is attached at the 2-, 3-, 4-, etc. positions) to yield glucose or galactose as opposed to glucoside or galactoside). For example, the intersaccharide linkages may be between one position of the additional saccharide units and the 2-, 3-, 4- and / or 6-positions of the preceding saccharide units.

Alternatively, but less desirable, there may be a polyalkylene oxide chain linking the hydrophobic moiety and the polysaccharide moiety. A preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched, containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group may contain up to about 3 hydroxyl groups and / or the polyalkylene oxide chain may contain up to about 10, preferably less than 5, alkylene oxide moieties. Suitable alkylpolysaccharides are octyl, nonydecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucose, fructosides, fructosides, fructosides, fructosides, fructosides, fructosides, fructosides, fructosides, fructosides and galactosides. Suitable mixtures include coconut alkyl, di-, tri-, tetra- and pentaglucosides and tallow alkyl-tetra-, penta- and hexaglucosides.

The preferred alkylpolyglycosides have the formula R2 O _(Cn H2 _n O) t (glycosyl) _x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl groups contain from about 10 to about 18, preferably odokolo 12 to about 14 carbon atoms, n is 2 or 3, preferably 2, t is from 0 to about 10, preferably 0 and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, and most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, an alcohol or an alkylpolyethoxy alcohol is first formed and then formed

SK 279651-6 reacts with glucose or glucose source to form a glucoside (attachment at 1-). The additional glycosyl units may then be attached between their 1-position and their previous 2-, 3-, 4- or 6-glycosyl unit position, preferably the 2- position.

7. Fatty acid amide surfactants having the formula:

ABOUT

II ^Rf: CN (R 7) 2, wherein R b is alkyl having from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R7 is selected from the group consisting of hydrogen, C j -C 4 alkyl, C 1 -C 4 hydroxyalkyl and - (C ₂ H ₄ O) _X II, wherein x varies from about 1 to about 3. Preferred amides are C 8 -C ₂ ammonium amides, monoethanolamides, diethanolamides and isopropanolamides.

Cationic surfactants may also be included in the detergent compositions of the invention. Cationic surfactants include ammonium surfactants such as alkyldimethylammonium halides, and these surfactants have the formula: [R2 (OR3) _x ] [R4 (OR3) _x ] ₂ R5N + X-, wherein R2 is an alkyl or alkylbenzyl group having from about 8 up to about 18 carbon atoms in the alkyl chain, wherein each R 3 is selected from the group consisting of -CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) -, -CH ₂ CH (CH ₂ OH) -, -CH ₂ CH ₂ CH ₂ - and mixtures thereof, wherein each R ⁴ is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl, ring structures formed by joining two groups R ⁴ , -CH ₂ CnOHCHOHCORbCHOHCH ₂ OH, wherein R b is any hexose or hexose polymer having a relative molecular weight of less than about 1000 and hydrogen when y is not 0; R 5 is the same as R 5 or is an alkyl chain wherein the total number of carbon atoms R ² plus r ⁵ is not more than 18; wherein each y is from 0 to about 10 and the sum of the y values is from 0 to about 151 and X is any compatible anion.

Other cationic surfactants useful herein are also described in U.S. Pat. No. 4,228,044, issued Oct. 14, 1980, which is incorporated herein by reference.

In addition, other surfactants may be included in the detergent compositions of the invention. These include ampholytic surfactants. These surfactants may be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic and tertiary amines in which the aliphatic group may have a straight or branched chain. One of the aliphatic substituents contains at least 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic solubilizing group for dissolution in water, for example a carboxyl, sulfonate or sulfate group. Examples of amphblytic surfactants are disclosed in U.S. Pat. No. 3,929,678, issued December 30, 1975; 19, r. 18-35, which is incorporated herein by reference.

Zwitterionic surfactants can also be included in the detergent compositions of the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Examples of zwitterionic surfactants are disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975, et al. 19, r. 38 to stí. 22, r. 48, which is incorporated herein by reference.

Ampholithic surfactants and surfactant ions are generally used in combination with one or more ionic and / or nonionic surfactants.

The detergent compositions of the invention may also contain auxiliary builders, including both inorganic and organic detergent builders to assist in controlling mineral hardness. Typical amounts of the auxiliary activator are from about 5% to about 200% by weight of the zeolite / layered silicate activator.

Inorganic builders include, but are not limited to, alkali metal mixtures, ammonium salts, and alkanolammonium salts of polyphosphates (e.g., tripolyphosphates, pyrophosphates, and glass polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates) , sulfonates and aluminosilicates. Borate activating agents as well as activating agents containing borate-forming materials that can form borate under detergent storage or washing conditions (hereinafter collectively referred to as borate activating agents) may also be used. Preferably, non-borate builders are used in the compositions of the invention for use at washing temperatures below about 50 ° C, particularly below about 40 ° C.

Examples of silicate builders are alkali metal silicates, especially those having a SiO ₂ : Na ₂ O ratio in the range of 1.6: 1 to 3.2: 1. However, other silicates, such as magnesium silicate, which may serve as a gelling agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component in a foam control system.

Aluminosilicates other than zeolites may also be used. Generally, the aluminosilicates will have an empirical formula of M ₂ (zA 10 ₂ .ySiO ₂ ), wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, although not necessarily within the scope of the formulas established in the description of zeolites.

Examples of carbonate builders are alkali metal carbonates, including sodium carbonate and sodium sesquicarbonate, and mixtures thereof, and ultrafine calcium carbonate, as described in German patent specification no. No. 2 321 001, published Nov. 15, 1973, to which Sata is referred to as part of the description.

Phosphate and phosphonate builders may be added, although it is generally desired to replace these builders with zeolite / layered silicate builders and optionally other builders and detergent builders. If so, they are preferably present only at low levels. Preferably, the phosphate activating additive constitutes less than about 10%, more preferably less than about 5% and most preferably substantially 0 percent by weight of the total activating additive in the composition.

Particular examples of polyphosphates are alkali metal, sodium, potassium and ammonium pyrophosphate tripolyphosphates, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetaphosphate, in which the degree of polymerization

It ranges from about 6 to about 21 and the phytic acid salt.

Examples of phosphonate salt activating agents are the water-soluble salts of ethane-1-hydroxy-1,1-diphosphonate, especially the sodium and potassium salts, the water-soluble salts of methylenedisulfonic acid, for example the tri-sodium and tri-potassium salts and the water-soluble salts. salts of substituted methylenediphosphonic acids such as ethylidene-, isopropylidene-, benzylidene-phosphonate tri-sodium or tri-potassium, and halogenomethylidene phosphonates. Phosphonate salt activating agents of this type are described in U.S. Pat. Nos. 3,159,581, issued Dec. 1, 1964, and 3,213,030, issued on Oct. 19, 1965, U.S. Pat. No. 3,422,021, issued Jan. 14, 1969, U.S. Pat. No. 3,400,148, issued September 3, 1968, and U.S. Pat. 14 January 1969, incorporated herein by reference.

Organic detergent builders suitable for the purposes of the invention include, but are not limited to, a wide variety of polycarboxylate compounds. The term polycarboxylate herein refers to compounds having multiple carboxyl groups, preferably at least 3 carboxylates.

As a rule, the polycarboxylate builder can be added to the composition in acid form, but can also be added in the form of a neutralized soluble salt. When used in the form of salts, alkali metal salts (such as sodium, potassium and lithium or alkanolammonium salts) are preferred.

A variety of useful materials are included among the polycarboxylate builders. One important category of polycarboxylate builders includes etipoly carboxylates. A number of ether polycarboxylates have been described for use as detergent builders. Examples of useful ether polycarboxylates include oxydisuccinate as described in U.S. Pat. No. 3,128,287, issued April 6, 1964, and U.S. Pat. No. 3,635,830, issued Jan. 18, 1972, which is incorporated herein by reference.

A particular type of ether polycarboxylates useful as activating ingredient in the compositions of the invention also includes those having the general formula: CH (A) (COOX) -CH (COOX) -O-CH (COC> X) -CH (COOX) B, wherein A is H or OH; B is H or -O-CH (COOX) -CH 2 (COOX); and X is H or a salt-forming cation. For example, if in the above formulas parts A and B are equal to H, then the compound is oxydisuccinic acid and its water-soluble salts. If part A is OH and part B is H, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts. When part AH and part B are -O-CH (COOX) -CH ₂ (COOX), then the compound is tartrate disuccinic acid (TDS) and its water-soluble salts. The compositions of these activating ingredients are particularly suitable for use in the detergent compositions of the invention. Particularly suitable are mixtures of TMS and TDS in a weight ratio of TMS to TDS of from about 97: 3 to about 20: 80. These activating agents are disclosed in U.S. Pat. No. 4,663,071, issued May 5, 1987.

Suitable ether polycarboxylates also include cyclic compounds, especially alicyclic compounds such as those described in U.S. Pat. No. 3,923,679, 3,835,163,4,158,635, 4,120,874 and 4,102,903, all of which are incorporated herein by reference.

Other useful detergent builders include etherhydroxypolycarboxylates represented by the structure:

HO- [C (R) (COOM) -C (R) (COOM) -O] _n -H, wherein M is hydrogen or a cation forming the resulting salt in a water-soluble form, preferably an alkali metal, ammonium or substituted ammonium cation, n is from about 2 to about 15 (preferably n is from about 2 to about 10, more preferably n is on average from about 2 to about 4) and each R is identical or different and is selected from hydrogen, C 1 -C 4 alkyl or C 1 -C 4 substituted alkyl (preferably R is hydrogen).

Still other polycarboxylates include copolymers of maleic anhydride with ethylene or vinylethyl ether, 1,3,5-trihydroxybenzene-2,4,5-trisulfonic acid and carboxymethyloxysuccinic acid.

Organic polycarboxylate builders also include various alkali metals, ammonium and substituted ammonium salts of polyacetic acids. Examples include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid and nitrilotriacetic acid.

Polycarboxylates such as mellitic acid, succinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof are also suitable.

Citrates, e.g. citric acid and its soluble salts (especially sodium) are polycarboxylate builders of particular importance for high performance liquid detergent formulations, but can also be used in granular compositions.

Other carboxylate builders include the carboxylated sugars described in U.S. Pat. No. 3,723,322, issued Mar. 28, 1973, which is incorporated herein by reference.

Also suitable in the detergent compositions of the invention are 3,3-dicarboxy-4-oxa-1,6-hexanodioates and related compounds disclosed in U.S. Patent 4,566,984, issued January 29, 1986, which is incorporated herein by reference as to the description. Suitable succinic acid activating agents include C 5 -C 20 alkyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Alkylsuccinic acids typically have the general formula R-CH (COOH) CH 2 (COOH), i. succinic acid derivatives wherein R is a hydrocarbon, e.g. C 10 -C 20 alkyl or alkenyl, preferably C 12 -C 16, or wherein R may be substituted with hydroxyl or sulfo-, sulfoxy- or sulfone substituents, all of which are described in said patents.

Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.

Specific examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecyl succinate (most preferred), 2-pentadecenyl succinate and the like. Lauryl succinates are preferred activating ingredients in this group and are described in European Patent Application 86200690.5 / 0.200.236, published Nov. 5, 1986.

Examples of useful activating ingredients also include sodium and potassium carboxymethyloxymalonate, carboxymethylsuccinate, cis-cyclohexane hexacarboxylate, cis-cyclopentane tetracarboxylate, water-soluble polyacrylates (these polyacrylates, having relative molecular weights up to about 2000, can also be effectively used as dispersants) and copolymers of maleic anhydride with vinyl methyl ether or ethylene.

Other suitable polycarboxylates are the polyacetal carboxylates described in U.S. Pat. No. 4,144,226, issued

SK 279651-6

13.3.1979, to which we refer here as part of the description. These polyacetal carboxylates can be prepared by contacting each other under polymerization conditions with a glyoxylic acid ester and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in an alkaline solution, converted to the corresponding salt, and added to the surfactant.

Polycarboxylate activating agents are described in U.S. Pat. No. 3,308,067, issued March 7, 1967, the disclosure of which is incorporated herein by reference. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylene malonic acid.

Other activating ingredients known in the art may also be used, for example monocarboxylic acids and soluble salts thereof having long chain hydrocarbyls. These also include materials commonly referred to as soaps. Typically, chain lengths of Cκ-C qo are used. The hydrocarbyls may be saturated or unsaturated.

Enzymes for a variety of purposes, including protein, sugar or triglyceride based stain removal, and e.g. to prevent leakage of dye. The enzymes used may include proteases, amylases, lipases, cellulases and peroxidases, as well as mixtures thereof. They may be of any suitable origin, of plant, animal, bacterial, fungal or yeast origin. However, their choice is governed by a number of factors such as pH activity and / or optimum stability, thermal stability, stability with respect to the active detergents, activating additives, etc. In this regard, enzymes of bacterial and fungal origin, such as bacterial amylase and protease and fungal origin cellulase, are preferred.

Suitable examples of proteases are subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms. Another suitable protease is obtained from a Bacilus strain having a maximum activity in the pH range of 8-12, developed and sold by Novo Industries A / S pd. prot. no. Esperase. The preparation of this enzyme and analogous enzymes is described in British Pat. Proteolytic enzymes suitable for removing protein-based stains available on the market include those sold under the trade names ALCALASETM _and SAVINASE TM by Novo Industries A / S (Denmark) and MAXATASETM by Bio-synthetics, Inc. (Netherlands).

Of particular interest in the category of proteolytic enzymes, particularly for liquid detergent compositions, are the enzymes referred to herein as Protease A and Protease B. Protease A and methods for its preparation are described in European Patent Application 130,756, published January 9, 1985, which is hereby incorporated herein by reference. part of the description. Protease B is a proteolytic enzyme that differs from Protease A in that it has a tyrosine-substituted leucine at position 217 in its amino acid sequence. The enzyme Protease B is described in European patent application no. No. 130,756, published Jan. 9, 1985, which is incorporated herein by reference.

Amylases include, for example, alpha-amylases obtained from a particular strain of B. licheniforms, described in more detail in British Patent No. 5,960,549. No. 1,296,839, to which we have already referred as part of the description. Amylolytic proteins include, for example, _the compound RAPIDASETM d Intemational

Bio-Synthetics, Inc.. and TERMAMYL TM _{0 (} Novo Industries.

Cellulases useful in the present invention include cellulases of both bacterial and fungal origin. Preferably, they have an optimum pH between 5 and 9.5. Suitable cellulases are described in U.S. Pat. No. 4,435,307, issued March 6, 1984, which is incorporated herein by reference in its description, which describes cellulase of fungal origin made from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2 075 028 and GB-A-2 095 275 and DE-OS-2 247 832.

Examples of such cellulases are cellulases produced from Humicola Insolens (Humicola grisea var. Thermoidea), in particular Humicola DSM 1800, and celluloses produced by Bacilus N or cellulase-producing fungi 212 belonging to the genus Aeromonas and cellulases extracted from hepatopancreas sea mulch ).

Suitable lipase enzymes for use in detergents include lipases produced by microorganisms of the Pseudomonas family, such as Pseudomonas stutzeri ATCC 19.154, described in British Pat. 1 327 034, to which reference is made here. Suitable lipases include lipases having a positive immunological reaction with the lipase antibody produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase and the method for its production are described in Japanese Patent Application no. 53-20487, published Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co.Ltd., Japan under the designation Lipase P Amano, hereinafter referred to as Amano-P. Such lipases of the invention should have a positive immunological interaction with the Amano-P antibody, using the standard and well-known Ouchterlony immunodiffusion procedure (Acta. Med. Scan., 133, 76-79, 1950). These lipases and a method for their immunological interaction with Amano-P are also described in U.S. Pat. No. 4,707,291, issued Nov. 17, 1987, which is incorporated herein by reference. Typical examples of this lipase are Amano-P lipase, lipase ex Pseudomonas fragu FERM P 1339 (available under the designation Amano-B), lipase ex Pseudomonas nitroreducens var. lipolyticum FERM P 1338 (available under the designation Amano-CES), lipases ex Chiomobacter viscosum, e.g. Chromobacter viscosum var. Lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Japan 1 and further Chromobacter viscosum lipases from U. S. Biochemical Corp., USA and Disoynth Co., The Netherlands and lipases ex Pseudomonas gladioli.

Peroxidase enzymes are used in conjunction with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for bleaching the solution, i. j. to prevent transfer of dyes or pigments taken from the substrates during washing operations to other substrates in the wash solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO / 099813, published Oct. 19, 1989, which is incorporated herein by reference.

A wide variety of enzyme materials and compositions for incorporating them into synthetic detergent granules are also described in U.S. Pat. No. 3,553,139, issued Jan. 5, 1971, the disclosure of which is incorporated herein by reference. Enzymes are further described in U.S. Pat.

SK 279651Β6

No. 101,457, issued Jul. 18, 1978, and U.S. Pat. No. 4,507,219, issued Mar. 26, 1985, which is incorporated herein by reference. Enzyme materials useful for liquid detergent formulations and their incorporation into such formulations are described in U.S. Pat. No. 4,261,868, issued Apr. 14, 1981, which is incorporated herein by reference.

Enzymes are normally incorporated in amounts sufficient to provide up to about 5 mg by weight, more typically from about 0.05 mg to about 3 mg, of active enzyme per gram of composition.

For granular detergents, the enzymes are preferably coated or formulated into beads using enzyme-inert additives to minimize dust formation and improve storage stability. Methods for achieving this goal are well known in the art. Stabilization procedures for enzymes are preferably used in liquid formulations. For example, one method of stabilizing the enzyme in aqueous solutions involves the use of free calcium ions from a source such as calcium acetate, calcium formate and calcium proprionate. Calcium ions can be used in combination with salts of short-chain carboxylic acids, for example, formates, see e.g. U.S. Pat. No. 4,318,818, issued March 9, 1982, which is incorporated herein by reference. It has also been proposed to use polyols such as glycerol and sorbitol, alkoxy alcohols, dialkyl glycoethers, mixtures of polyhydric alcohols with polyfunctional aliphatic amines (e.g. alkanolamines such as diethanolamine, triethanolamine, di-isopropanolamine, etc.) and alkali metal borate or borate. Enzyme stabilization procedures are further described and exemplified in U.S. Pat. No. 4,261,868, issued Apr. 14, 1981, and U.S. Pat. No. 3,600,319, issued Aug. 17, 1971, both of which are incorporated herein by reference and published on Oct. 29, 1986. Preference is given to stabilizers containing no boric acid and borates. Enzyme stabilization systems are also described e.g. U.S. Pat. 4 261 868, no. 3,600,319 and no. 3,519,570.

The detergent compositions of the invention may comprise bleaches and bleaching compositions comprising a bleach and one or more bleach activators. If present, the bleaching compounds will typically be comprised at levels of from about 1% to about 20%, more typically from about 1% to about 10% of the detergent composition. Generally, bleaching compounds are in non-liquid formulations, e.g. granular formulations, optional ingredients. If present, the bleach activator content will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition.

The bleaches used in the compositions of the invention may be any bleaches suitable for detergent compositions in textile cleaning, hard surface cleaning, or any other cleaning purposes that are now known. These include oxygen bleaches as well as other bleaches. For washing conditions below about 50 ° C, in particular below about 40 ° C, it is preferred that the compositions of the invention do not contain borates or a material that can form borate on site under detergent storage and washing conditions. Under these conditions, it is therefore preferred whether a borate-free bleach or a borate-free bleach is used. Preferably, the detergents for use at these temperatures are substantially free of borates or borate-forming materials. In this context, substantially free of borates or borate-forming materials is meant that the composition comprises no more than about 2 wt. % of any type of borate containing or forming material and preferably no more than 1%, more preferably 0%.

One category of bleach that can be used includes peroxycarboxylic acid bleaches and salts thereof. Suitable examples of this class of bleach include monoperoxyilate hexahydrate, magnesium salt of metachloroperbenzic acid, 4-nonylamino-4-oxoperoxybutyric acid, and diperoxydodecadioic acid. Such bleaches are described in U.S. Pat. No. 4,483,781, issued Nov. 20, 1984, to U.S. Pat. 740,446, filed Jun. 3, 1985, European Patent Application 0 133 354, published Feb. 20, 1985, and U.S. Pat. No. 4,412,934, issued Nov. 1, 1983, all of which are incorporated herein by reference. Preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Pat. No. 4,634,551, issued Jan. 6, 1987, which is incorporated herein by reference.

Another category of bleaches that can be used includes halogen bleaches. Examples of hypohalite bleaches include, for example, trichloroisocyanuric acid and sodium and potassium dichloroisocyanurates and N-chloro- and N-bromo-alkanesulfonamides. Such materials are normally added in an amount of 0.5-10 wt. % of the finished product, preferably 1-5 wt. %.

Peroxide bleaches may also be used. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.

The peroxygen bleaches are preferably combined with bleach activators which result in the formation of the peracid corresponding to the bleach activator directly in the aqueous solution (i.e. during the wash process).

Preferred bleach activators incorporated into the compositions of the invention have the general formula:

ABOUT

II

R = C-L, wherein R is an alkyl group containing from about 1 to about 18 carbon atoms, the longest linear alkyl chain extending from and including the carbonyl carbon contains from about 6 to about 10 carbon atoms and L is a leaving group wherein the conjugated acid has a pKa ranging from about 4 to about 13. These activators are described in U.S. Pat. No. 4,915,854, issued April 10, 1990, which is incorporated herein by reference, and in U.S. Pat. No. 4,412,934, to which we have already referred.

Bleaching agents other than oxygen bleaches are also known in the art and can be used in the present case. One type of non-oxygen bleach that is of particular interest includes photoactivated bleaches such as sulfonated zinc and aluminum phthalocyanines. These materials can be deposited on the substrate during the wash process. Upon irradiation with light, in the presence of oxygen, such as after daylight drying, the sulfonated zinc phthalocyanine is activated and as a result the substrate is whitened. A preferred zinc phthalocyanine and photoactivated bleaching process is described in U.S. Pat. No. 4,033,718, issued Jan. 5,1977, to whom

SK 279651 Β6 is incorporated herein by reference. Typically, detergent compositions will contain from about 0.025% to about 1.25% by weight of sulfonated zinc phthalocyanine.

Any soil release agents known to those skilled in the art may be used to practice the invention. The polymeric soil release agents are characterized by having hydrophilic segments for hydrophilizing the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments for storage on hydrophobic fibers and to remain adhered during the completion of washing or rinsing cycles so as to anchor for hydrophilic segments. This will allow stains appearing after treatment with the soil release agent to be easier to clean in later washing procedures.

While it may be beneficial to use polymeric soil release agents in any of the detergent compositions discussed herein, particularly those compositions used for laundry and other uses where grease and oil needs to be removed from hydrophobic surfaces, may increase the effectiveness of many of the more commonly used types polymeric soil release agents the presence of polyhydroxy fatty acid amide in detergent compositions. The anionic surfactants interfere with the ability of certain soil release agents to deposit and remain on hydrophobic surfaces. These polymeric soil release agents have nonionic hydrophilic segments or hydrophobic segments that interact with anionic surfactants.

Compositions in which an improved soil release agent efficiency using a polyhydroxy fatty acid amide can be obtained are those comprising an anionic surfactant system, a soil release agent interacting with the anionic surfactant, and an amount of polyhydroxy fatty acid amide. a fatty acid (PFA) promoting soil release agent, wherein (I) the interaction between the soil release agent and the anionic surfactant system of the detergent composition can be illustrated by comparing the level of soil release agent (SRA) deposition on hydrophobic fibers (e.g., polyester) in an aqueous solution between (A) a control assay that measures the deposition of an SRA detergent composition in an aqueous solution in the absence of additional detergent ingredients, and (B) an SRA / anionic surfactant assay wherein the same type and multiplicity The anionic surfactant system used in the detergent composition combines in aqueous solution with SRA, at the same weight ratio of SRA to the anionic surfactant system of the detergent composition, with reduced deposition in (B) relative to (A) showing anionic surfactant interaction an active agent; and (Π) whether the detergent composition comprises an amount of a polyhydroxy fatty acid amide promoting soil release agent can be determined by comparing the SRA deposition of the SRA / anionic surfactant of (B) with the deposition of the soil release agent in (C) in SRA / anionic. surfactant / PFA assay, where the same level of polyhydroxy fatty acid amide detergent composition is combined with the soil release agent and the anionic surfactant system corresponding to said SRA / anionic surfactant, wherein improved deposition of the soil release agent in the assay ( C) with respect to Test (B), indicates that an amount of a polyhydroxy fatty acid amide supporting the soil release agent is present. For this purpose, the tests should be performed at anionic surfactant concentrations in aqueous solution that are above the critical micelle concentration (CMC) of the anionic surfactant and preferably above 100 parts per million. The concentration of the polymeric soil release agent should be at least 15 parts per million. A sample of semi-finished fabric should be used as the source of hydrophobic fibers. The same samples are immersed and mixed in aqueous solutions at 35 ° C for the respective tests for 12 minutes, then removed and analyzed. The level of deposition of the polymeric soil release agent can be determined by labeling the reagent prior to treating the sample with radiation and then conducting radiochemical analysis by methods known in the art.

As an alternative to the radiochemical analytical methodology described, deposition of the soil release agent can be determined alternatively in the above assays (i.e., A, B and C) by determining the absorbency of the solutions with respect to ultraviolet light (UV) according to methods well known in the art. The reduced UV absorption in the test solution after removal of the hydrophobic fibrous material corresponds to the increased SRA delay. As will be appreciated by those skilled in the art, UV analysis should not be used for test solutions containing material types and levels that cause excessive UV absorption interference, such as high levels of surfactants with aromatic groups (e.g., alkylbenzenesulfonates, etc.)

Thus, the amount of soil release agent in the polyhydroxy fatty acid amide is understood to mean the amount of a surfactant that will promote the deposition of the soil release agent on the hydrophobic fibers as described, or an amount that can improve the grease cleaning performance. / ointments for fabrics washed in said detergent composition in a subsequent cleaning operation.

The amount of polyhydroxy fatty acid amide required to promote deposition will vary with the selected anionic surfactant, the amount of anionic surfactant, particularly the selected soil release agent, and particularly the polyhydroxy fatty acid amide. Generally, the compositions will contain from about 0.01% to about 10% by weight of the soil release polymer, more typically from about 0.1% to about 5% and from about 4% to about 50%, more typically from about 5% to about 30%. % anionic surfactant. Such a composition should generally contain at least about 1%, preferably at least about 3% by weight of the polyhydroxy fatty acid amide, although the solution is not limited to such a case.

Polymeric soil release agents in which efficiency is enhanced by polyhydroxy fatty acid amide in the presence of an anionic surfactant include soil release agents having: (a) one or more ionic hydrophilic components consisting essentially of (1) polyoxyethylene segments having a degree of polymerization at least 2, or (2) oxypropyl12

2796 new or polyoxypropylene segments having a degree of polymerization of from 2 to 110, said hydrophilic segment comprising no oxypropylene unit, unless bound to adjacent portions at each end by ether bonds, or (3) a mixture of oxyalkylene units containing oxyethylene and from 1 to about 30 oxypropylene units, said mixture comprising sufficient oxyethylene units such that the hydrophilic component has a hydrophilicity sufficiently large to increase the hydrophilicity of conventional polyester synthetic fiber surfaces when depositing a soil release agent on such a surface, said hydrophilic segments preferably containing at least 25% oxyethylene units; more preferably, in particular for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more hydrophilic components comprising (1) C3 oxyalkylene terephthalate segments, wherein, where said hydrophobic components also contain oxyethylene terephthalate, the ratio of oxyethylene terephthalate: C3 oxyalkylene terephthalate units is 2: 1 or less, (2) C4-C6 alkylene or C4-C6 oxyalkylene segments or mixtures thereof, (3) poly (vinyl ester) segments, preferably poly (vinyl acetate) segments, having a degree of polymerization of at least 2 or (4) C1-C4 alkyl ether or C4 hydroxyalkyl substituents or mixtures thereof, said substituents being present in the form of C1-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives or mixtures thereof, and such cellulose derivatives are amphiphilic so that they have a sufficient level of C1-C4 alkyl ether and / or C4 hydroxyalkyl units to deposit on conventional polyester synthetic fiber surfaces and maintain a sufficient level of hydroxyl content , once p they adhere to such a surface of conventional synthetic fibers to increase the surface hydrophilicity of the fibers or combinations (a) and (b).

Typically, polyoxyethylene segments (a) (1) will have a degree of polymerization of from about 2 to about 200, although higher levels, preferably from about 3 to about 150, more preferably from about 6 to about 100, can be used. Suitable C4-C6oxyalkylene hydrophobic segments include , but not are not limited to, end polymeric soil release agents such as MO3S _(CH2) n OCH ₂ CH ₂ O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent . No. 4,721,580, the disclosure of which is incorporated herein by reference.

Polymeric soil release agents useful in the present invention include cellulose derivatives such as hydroxyether cellulose polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polyethylene oxide terephthalate, and the like.

Cellulose derivatives that are functional as soil release agents are commercially available and include cellulose hydroxyethers such as Methocel (R) (Dow).

Cellulosic soil release agents for use in the present invention also include those selected from the group consisting of C 1 -C 4 alkyl- and C 4 hydroxyalkylcelluloses such as methylcellulose, ethylcellulose, hydroxypropylmethylcellulose and hydroxybutylmethylcellulose. A variety of cellulose derivatives useful as soil release agents are described in U.S. Pat. No. 4,000,093 of Dec. 28, 1976, which is incorporated herein by reference.

The soil release agents marked with poly (vinyl ester) hydrophobic segments include graft copolymers of poly (vinyl ester), for example, C 1 -C 8 vinyl esters, preferably poly (vinyl acetate) grafted on polyalkylene oxide backbone, such as polyethylene oxide backbones. Such materials are known in the art, and are described in European Patent Application 0 219 048, published 22/01987. Suitable commercially available soil release agents of this kind include Sokalan ™ type materials, e.g. Sokalan ® M HP-22, available from BASF (Germany).

One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and ethylene oxide (PEO) terephthalate. More specifically, the polymers are comprised of repeating units of ethylene terephthalate and PEO terephthalate in a molar ratio of ethylene terephthalate units to PEO terephthalate units of from about 25: 75 to about 35: 65, said polyethylene oxide containing PEO terephthalate units having relative molecular weights of from about 300 to about 2000. The relative molecular weight of this soil release agent is in the range of about 25,000 to about 55,000. See also U.S. Pat. No. 3,959,230, issued Jan. 25,1976, incorporated herein by reference. Similar copolymers are also described in U.S. Pat. No. 3,893,929, issued July 8, 1975, which is also incorporated herein by reference.

Another preferred polymeric soil release agent is polyester with repeating units in the form of ethylene terephthalate units containing 10 to 15 wt. % ethylene terephthalate units together with 90 to 80 wt. % of polyoxyethylene terephthalate units derived from polyoxyethylene glycol of an average molecular weight of 300-5000 and the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the polymer compound is between 2: 1 and 6: 1. Examples of this polymer include 512R available from Dupont® ICI. These polymers and methods for their preparation are described in more detail in U.S. Pat. No. 4,702,857, issued Oct. 27, 1987, which is incorporated herein by reference.

Another preferred polymeric soil release agent is a sulfone product of a suitably linear ester oligomer, consisting of an oligomeric ester backbone of terephthaloyl and oxyalkyleoxy repeating units and end portions covalently attached to the backbone, said soil release agent being derived from an alkyl alcohol ethoxylate, dimethyl ethoxylate, dimethyl ethoxylate, 2 propylenediol, wherein after sulfonation the terminal portions of each oligomer have an average of from about 1 to about 4 sulfonated groups in total. These soil release agents are described in more detail in U.S. Pat. No. 4,986,451, issued Nov. 6, 1990, which is incorporated herein by reference.

Other suitable polymeric soil release agents include 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters terminated with ethyl or methyl groups, as described in U.S. Pat. No. 4,711,730, issued Dec. 8, 1987, anionically terminated oligomeric esters according to U.S. Pat. No. 4,721,580, issued

26. 1. 1988, where the anionic endings are formed by sulfopolyethoxy groups derived from polyethylene13

2796 glycol (PEG) block polyester oligomer compounds of U.S. Pat. No. 4,702,857, issued Oct. 27, 1987, having a polyethoxy terminus of formula X- (OCH 2 CH 2) n - wherein n is from 12 to about 43 and X is C 1 -C 4 alkyl or preferably methyl, all of which are incorporated herein by reference. as part of the description.

Other polymeric soil release agents include the soil release agents of U.S. Pat. No. 4,877,896, issued Oct. 31, 1989, which discloses anionically terminated terephthalate esters, particularly sulfoaroyl, the disclosure of which is incorporated herein by reference. The terephthalate esters contain unsymmetrically substituted oxy-L 2 -alkyleneoxy units. Among the soil release agents of U.S. Pat. No. 4,877,896 includes materials with polyoxyethylene hydrophilic components or C3 oxyalkylene terephthalate (propylene terephthalate) repeating units within the range of hydrophobic components of (b) (1) mentioned. They are soil release agents characterized by either or both of the above criteria, which particularly benefit from the addition of polyhydroxy fatty acid amides in the presence of anionic surfactants to the compositions of the invention.

If used, soil release agents will generally comprise from about 0.01% to about 10.0% by weight of the detergent compositions, typically from about 0.1% to about 5%, preferably from about 0.2% to about 5%. 3.0%.

The detergent compositions of the invention may also optionally contain one or more ferrous or manganese chelating agents as a supplement to the activating additive. Such chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof, as all hereinafter defined. Without wishing to be bound by theory, it is believed that the utility of these materials derives in part from their extraordinary ability to remove iron and manganese ions from washing solutions by forming soluble chelates.

Aminocarboxylates suitable as optional chelating agents in the compositions of the invention may have one or more, preferably at least two, substructure units

CH ₂ \

N - (CH 2) x -COOM, wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and x is from 1 to about 3, preferably 1. Preferably, these aminocarboxylates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Useful aminocarboxylates include ethylenediaminetetraacetates, N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraamine hexaacetates, diethylenetriaminepentaacetates and ethanediglycine salts, and their ammonium salts and their ammonium salts, their salts.

Aminophosphates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are allowed in the detergent compositions. Compounds with one or more, preferably at least two, units of the structure are suitable

CH;

XN - (CH ₂ ) _x - PO 3 M ₂ , Z wherein M is hydrogen, an alkali metal, ammonium or substituted ammonium and x is from 1 to about 3, preferably 1, including ethylenediaminetetrakis (methylene phosphonates), nitrilotris (methylene phosphonates) and diethylenetriamine pentenisinisentisisakis . Preferably, these aminotosphonates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms. Alkylene groups can be shared by substructures.

Polyfunctionally substituted aromatic chelating agents are also useful in the compositions of the invention. These materials may include compounds having the general formula:

OH

R wherein at least one R is -SO 3 H or -COOH, or soluble salts and mixtures thereof. U.S. Pat. No. 3,812,044, issued Jan. 21,1974, incorporated herein by reference, discloses polyfunctionally substituted aromatic chelating agents and shading agents. Preferred compounds of this type in acid form are dihydroxysulfobenzenes such as 1,2-dihydroxy-3,5-disultobenzene. The alkaline detergent compositions may contain these materials in the form of an alkali metal salt, ammonium or substituted ammonium (e.g., mono- or triethanolamine salts).

When used, the chelating agents will generally comprise from about 0.1% to about 10% by weight. % of detergent compositions. More preferably, the chelating agents will contain from about 0.1% to about 3.0% by weight of such compounds.

The compositions of the invention may also optionally contain water-soluble ethoxylated amines having ileate removal and anti-deposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of water-soluble ethoxylated amines. Liquid detergent compositions will typically contain from about 0.01% to about 5%. These compounds are selected from the group consisting of:

(1) ethoxylated monoamines having the formula: (XL) -N- (R2) ₂ , (2) ethoxylated diamines having the formula:

R 2 N-R 1 -N-R 2 (R ₂ ) ₂ -N-R 1 -N (r 2) ₂ I 1 1 L L ι i 1 L 1 1 1 x x 1 X or (X-L-) 2-N-R-N (R 2) 2,

(3) ethoxylated polyamines having the formula:

R 2

I

R3 - [(At) q - (R4) _t -NL.X] _p , (4) ethoxylated amine polymers having the general formula:

SK 279651-6

R 2 [(R ² ) 2 -NJ _w (R 1 -N) x (R 1 -N) _y (R 1 -NX) _z

L 1 X and (5) mixtures thereof, wherein A1 is 0 O 0 0 0 s II II II / -NC-. and -NCO-, -NCN-, -CN, -OCN-. 1 R I 1 1 R R R 1 R R ABOUT O O O O II II II II 1 -WHAT- -OCO- -OC- -ΟΝΟ- Ι R

or -O-; R is H or C 1 -C 4 alkyl or hydroxyalkyl; R1 is a C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units, provided that no ON bonds are formed; each R2 is C4-C4 or hydroxyalkyl, -LX or two R2 together with - (CH2) r, -A2- (CH2) _s , wherein A2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2 and r + s is 3 or 4; X is a nonionic group, an anionic group or mixtures thereof, R 3 is a substituted C 3 -C 12 alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having substitution positions; is a C1-C12 alkylene, hydroxyalkylene, alkenyl, rylene or alkarylene or a C2-C3 oxyalkylenyl moiety having from 2 to 20 oxyalkylene units, provided that no O-O or ON bonds are formed; L is a hydrophilic chain that contains a polyoxyalkylene moiety - [(R ⁵⁰ O) m (CH 2 CH 2 O) n -, wherein R ⁵ is C 3 -C 4 alkylene or hydroxyalkylene amine such that the moiety - (CH 2 CH 2 O) n - contains at least about 50 weight. % of said polyoxyalkylene moiety; for said monoamines, m is from 0 to about 4, n is at least about 12; for said diamines, m is from 0 to about 3 and n is at least about 6 when R 1 is C 2 -C 3 alkylene, hydroxyalkylene or alkenylene and at least about 3 when R 1 is other than C 2 -C 3 alkylene, hydroxyalkylene or alkenylene; for said polyamine and amine polymers, m is from 0 to about 10 and n is at least 3; p is from 3 to 8, q is 1 or 0, provided that t is 1 when q is 1; w is 1 or 0; x + y + at least 2; and y + z is at least 2. The most preferred agent for releasing impurities and preventing their re-deposition is ethoxylated tetraethylenepentamine. Exemplary amines are further described in U.S. Pat. No. 4,579,898, issued Jul. 1, 1986, which is incorporated herein by reference. Another group of preferred agents for the removal of clay impurities and to prevent their re-deposition are the cationic compounds described in European Patent Application no. No. 111,965, published Jun. 27, 1984, which is incorporated herein by reference. Other clay soil removal and re-deposition agents include the ethoxylated amine polymers described in European patent application no. 111 984, published Jun. 27, 1984, zwitterionic polymers, described in European Patent Application Ser. 112,592 published Jul. 4, 1984; and amine oxides disclosed in U.S. Pat. No. 4,548,744, issued

October 22, 1985, all of which are incorporated herein by reference.

Other agents may also be used in the compositions of the invention to remove clay impurities and prevent their re-deposition. Another type of preferred reagent of this type includes carboxymethylcellulose (CNC) materials. These materials are well known in the art.

Polymeric dispersing agents may advantageously be used in the compositions of the invention. These materials can assist in controlling calcium and magnesium hardness. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although other materials known in the art may also be used. Without wishing to be bound by the theory, it is believed that polymeric dispersants promote the overall performance of a detergent activator when used in combination with other activating ingredients (including lower molecular weight polycarboxylates), inhibiting crystal growth, particle debris, and particle retardation saving again.

Polymeric dispersing agents are generally used in amounts of from about 0.5% to about 5% by weight of the detergent composition, more usually from about 1.0% to about 2.0%.

The polycarboxylate materials that can be used as the polymer dispersing agent in the compositions of the invention are these polymers or polymers containing at least about 60 wt. % of general formula segments:

wherein X, Y and Z are each selected from the group consisting of hydrogen, methyl, carboxyl, carboxymethyl, hydroxyl and hydroxymethyl, a salt-forming cation and is from about 30 to about 400. Preferably X is hydrogen or hydroxyl, Y is hydrogen or carboxyl, Z is hydrogen and M is hydrogen, alkali metal, ammonium or substituted ammonium.

Polymeric polycarboxylate materials of this type can be prepared by polymerizing or polymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated acid monomers that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, and methylene malonic acid. The presence of monomeric segments containing no carboxyl radicals, such as trimethyl ether, sylene, ethylene, etc., in the polymeric polycarboxylates used herein is suitable provided that such segments do not constitute more than about 40 wt. %.

Particularly suitable polymeric polycarboxylates may be derived from acrylic acid. Such acrylic acid-based polymers useful in the compositions of the invention are the water-soluble salts of polymerized acrylic acid. The average relative molecular weight of such polymers in acid form preferably ranges from about 2000 to 10,000, more preferably from about 4000 to 7000, and most preferably from about 4000 to about 5000.

The water-soluble salts of such acrylic acid polymers may include, for example, alkali metal salts, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polycarboxylate in this type in detergent compositions is described, for example, in U.S. Pat. 3,308,067, issued 7, 3, 1967, to which ¹ herein by reference as part of the disclosure.

Also, copolymers based on acrylic acid and maleic acid may be used as a preferred component of the dispersant and anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average relative molecular weight of such copolymers in acid form is preferably from about 2000 to about 100,000, preferably from about 5000 to 75,000, most preferably from about 7,000 to about 65,000. The ratio of acrylate segments to maleic segments in the copolymers will generally range from about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1. The water-soluble salts of such acrylic and maleic acid copolymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Soluble copolymers of acrylate and maleate of this type are known materials and are described in European patent application no. No. 66915, published Dec. 15, 1982, which is incorporated herein by reference.

Another polymeric material that may be included is polyethylene glycol (PEG). PEG may be characterized by the effective properties of a dispersing agent, as well as acting as an agent for removing clay impurities and preventing re-deposition. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1000 to about 50,000, and most preferably from about 1,500 to about 10,000.

Furthermore, any brightening or bleaching agents known in the art may be incorporated into the detergent composition of the invention.

The choice of a brightener for use in detergent compositions will depend on a number of factors such as the type of detergent, the nature of the other ingredients present in the detergent composition, the wash water temperature, the degree of mixing and the ratio of wash material to tank size.

The choice of brightener will also depend on the type of material to be cleaned, such as whether it is cotton, synthetic fabrics, etc. Since most detergent products are used to clean a variety of fabrics, the detergent compositions should contain a mixture of brighteners that will be effective for various fabrics. It is of course necessary that the individual components of such a brightener mixture be compatible with each other.

The commercially available optical brighteners which can be used according to the invention can be classified into two subgroups, including, but not limited to, stilbene derivatives, pyrozoline, coumarin, carboxylic acid, methincanines, dibenzotifen-5,5 -dioxide, azoles, 5- and 6-membered ring heterocycles and other miscellaneous reagents. Examples of such brighteners are described in M. Zahradnik's The Production and Application of Fluorescent Brightening Agents, published by Johl Wiley &amp; Sons, New York, 1983, which is incorporated herein by reference.

Stilbene derivatives which may be used in the present invention include, but are not limited to, bis (triazinyl) amino-stilbene derivatives; bisacylamine derivatives of stilbene; triazole derivatives of stilbene, oxadiazole derivatives of stilbene; oxazole derivatives of stilbene; and styryl derivatives of stilbene.

Some bis (triazinyl) aminostylbene derivatives that can be used in the present invention can be prepared from 4,4'-diamine-stilbene-2,2'-disulfonic acid.

Coumarin derivatives which may be used in the present invention include, but are not limited to, derivatives substituted in the third position, in the seventh position, and in the third and seventh positions.

Carboxylic acid derivatives that may be used in the present invention include, but are not limited to, filmaric acid derivatives, benzoic acid derivatives, p-phenyl-bis-acrylic acid derivatives, naphthalenecarboxylic acid derivatives, heterocyclic acid derivatives and cinnamic acid derivatives.

Cinnamic acid derivatives which can be used in the present invention can be further classified into groups including, but not limited to, cinnamic acid derivatives, styrazoles, styrylbenzofurans, styryloxadiazoles, styryltriazoles and styrylpolyphenyls, as described on p. . 77 of the cited publication by Zahradnik.

The styryzoles can be further classified into styrylbenzoxazoles, styrylimidazoles and styrylthiazoles as described on page 14. 78 cited publication by Zahradnik. It will be understood that the three subclasses do not necessarily provide an exhaustive list of sub-groups into which the styrylazoles can be sorted.

Another class of optical brighteners that may be useful in the present invention are the dibenzothiophene-5,5-disoxide derivatives described on p. 741-749 Encyclopedia The Kirk Othmer Encyclopedia of Chemical Technology, Vol. 3, p. 737-750, J. Wiley and Sou filc., 1962, which are incorporated herein by reference and include 3,7-diaminodibenzothiophene-2,8-disulfonic acid-5,5-dioxide.

Another class of optical brighteners that can be used in the present invention includes azoles that are derivatives of 5-membered ring heterocycles. These can be further subdivided into monoazoles and bisazoles. Examples of monoazoles and bisazoles are given in the encyclopedia cited.

Another class of brighteners that can be used in the present invention are derivatives of the 6-membered ring heterocycles described in the cited encyclopedia. Examples of such compounds include brighteners derived from 4-aminonaphthalamide.

In addition to the brighteners described, a variety of other agents can also be used as brighteners. Examples of such various reagents are described on p. 93-95 cited by Zahradnik, and include 1-hydroxy-3,6,8-pyrenetri-sulfonic acid, 2,4-dimethoxy-11,3,5-triazin-6-yl-pyrene; 4,5-diphenylimidazolone disulfonic acid and pyrazoline-quinoline derivatives.

Other specific examples of optical brighteners that can be used in the present invention are those described in U.S. Pat. No. 4,790,856, issued December 13, 1988, to which Sata is referred to as part of the disclosure. These brighteners include a series of PhorwiteTM brighteners _from Verona. Other brighteners described in this literature include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM, available from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis, based in

SK 279651Β6

Italy; 2- (4-styryl-phenyl) -2H- naphthol [l, 2-d] triazoles; 4,4-bis (l, 2,3-triazol-2-yl) -stil- benes; 4,4'-bis (styryl) bis; and γ-aminocoumarins. Specific examples of such brighteners include 4-methyl-7-diethylaminocoumarin; 1,2-bis (benzimidazol-2-yl) -ethylene; 1,3-difenylfiazolíny; 2,5-bis (benzoxazol-2-yl) -thiophene; 2-styryl-naphth [l, 2-d] oxazole; and 2- (stilben-4-yl) -2H-naphtho [1,2-d] triazole.

Other optical brighteners that can be used in the present invention include those disclosed in U.S. Pat. No. 3,664,015, issued Feb. 29, 1972, which is incorporated herein by reference.

Compounds of the invention may further include compounds known or which have become known for reducing or suppressing the formation of foam. The incorporation of such materials, hereinafter referred to as suds suppressors, may be desirable since the polyhydroxy fatty acid amide surfactants of the compositions of the invention may increase the foam stability of the detergent compositions. Foam suppression can be particularly important when the detergent composition comprises a relatively high suds surfactant in combination with a polyhydroxy fatty acid amide surfactant. Such suppression is particularly desirable for compositions intended for use in front load automatic washing machines. These washing machines are typically characterized by having a laundry and washing water drum having a horizontal axis and rotating about this axis. This type of mixing can result in high foam formation and consequently reduced cleaning effect. The use of suds suppressors may also be of particular importance in hot water conditions and high surfactant concentrations.

A wide variety of materials can be used as suds suppressors in the compositions of the invention as suds suppressors. Foam supersors are well known to those skilled in the art. They are usually described, for example, in the Kirk Othemer Encyclopedia (Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Vol. 7, pp. 430-447, J. Wiley and Dons Inc., 1979). One category of particularly interesting suds suppressor comprises monocarboxylic fatty acids and soluble salts thereof. These materials are disclosed in U.S. Pat. No. 2,954,347, issued Sep. 27, 1960 to Wayne St.; John, referred to herein as part of the description. Monocarboxylic fatty acids and their reindeer, for use as a suds suppressor, typically have hydrocarbyl chains of 10 to about 24 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium salts and ammonium and alkanolammonium salts. These materials are preferred categories of suds supersor for detergent compositions.

The detergent compositions may also contain suds suppressors which are not surfactants. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g. triglycerides of fatty acids), fatty acid esters of monovalent alcohols, aliphatic C18-C4 () ketones (e.g. stearone), etc. Other suds inhibitors include N-alkylated aminotriazine such as tri- to hexa-alkyhnelamines or di- to tetra-alkyldiamine-chlorotriazines formed as products of two or three moles of a primary or secondary amine containing from 1 to 24 carbon atoms, propylene oxide and monostearyl oxide and monostearyl oxide. is monostearyl alcohol phosphate ester and monostearyl di phosphates and phosphate esters of an alkali metal (e.g., sodium, potassium and lithium). Hydrocarbons such as paraffin and halogen paraffin can be used in liquid form. Liquid hydrocarbons will be liquid at room temperature and atmospheric pressure and will have a pour point in the range of about -40 ° C to about 5 ° C and a minimum boiling point of no less than 110 ° C at atmospheric pressure. It is also known to use waxy hydrocarbons having preferably a melting point below about 100 ° C. Hydrocarbons constitute a preferred category of suds suppressors for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Pat. No. 4,265,779, issued May 5, 1981, which is incorporated herein by reference. Thus, hydrocarbons include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term paraffin used in this explanation of suds suppressors is meant to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors includes silicone suds suppressors. This category includes the use of polyorganosiloxane oils such as polydimethyldiloxane, a dispersion or emulsion of polyorganosiloxane oils or resins, and a combination of polyorganosiloxane with silica particles, wherein the polyorganosiloxane is chemisorbed or fused to silica. Silicone suds suppressors are well known in the art and are described, for example, in U.S. Pat. No. 4,265,779, issued May 5, 1981, and European Patent Application Ser. No. 89307851.9, published Feb. 7, 1990, which is incorporated herein by reference.

Other silicone suds suppressors are described in U.S. Pat. No. 3,455,839, which relates to compositions and methods for defoaming aqueous solutions by adding small amounts of polydimethylsiloxane fluids.

Mixtures of silicone and silanated silicon dioxide are described, for example, in German patent application DOS 2 124 526. Silicone antifoams and suds controlling agents in granular detergent compositions are described in U.S. Pat. No. 3,933,672 and U.S. Pat. No. 4,652,392, issued Mar. 24, 1998.

An example of a silicone-based suds suppressor for use in the compositions of the invention is an amount of suds suppressing agent, consisting essentially of:

(1) a polydimethylsiloxane liquid having a viscosity of around 20 cs. to about 1500 cs. at 25 ° C;

(2) from about 5 to about 50 parts per 100 parts by weight (1) siloxane resins composed of (CH 3) 3 SiO 2 / SiO 2 units of a ratio of (Cl 13) 3 SiO 2 / Si to SiO 2 units of from about 0.6: 1 to about 1.2: 1; and (3) from about 1 to about 20 parts per 100 parts by weight of (1) solid silica gel.

For any detergent compositions for use in automatic washing machines, foam should not be formed to the extent that it flows through the washing machine. The suds suppressors, when used, are preferably present in a suds suppressing amount. By "suds suppressor amount" is meant that the formulator of the composition can select the amount of such suds control agent so as to sufficiently control the suds to achieve a low sudsing detergent for use in automatic washing machines. The amount of suds control agent will vary according to the selected

Detergent surfactants. For example, with relatively high suds surfactants, relatively more suds control agent is used to achieve the desired suds control than with less suds surfactants. In general, a sufficient amount of suds suppressor should be incorporated into the low-foaming detergent compositions so that the foam formed during the washing cycle of the automatic washing machine (ie by mixing the detergent in aqueous solution at the intended wash temperature and concentration) does not exceed about 75% of the drum volume. determines the difference between the total volume of the drum and the water plus the laundry.

Typically, compositions of the invention will contain from 0% d to about 5% penema suppressor, the monocarboxylic fatty acids and salts thereof will typically be present in amounts up to about 5% by weight of the detergent composition. Preferably, from about 0.5% to about 3% of a fatty carboxylate suds suppressor is used. Silicone suds suppressors are typically used in amounts up to about 2.0% by weight of the detergent composition, although larger amounts may be used. This upper limit is of a practical nature since it is about keeping costs as low as possible and the efficiency of smaller amounts for efficient foaming management. Preferably, from about 0.01% to about 1% of a silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%. In this context, the percentages given include all silica that can be used in combination with polyorganosiloxanes, as well as other additive materials that can be used. Typically, monostearyl phosphates are used at levels of from about 0.1% to about 2% by weight of the composition.

Hydrocarbon suds suppressors are typically used in amounts of from about 0.01% to about 5.0%, although higher amounts may be used.

Finally, a number of other ingredients may be included in the compositions of the invention, including other active ingredients, carriers, hydrotopes, processing aids, dyes and pigments, solvents for liquid formulations, and the like.

Liquid detergent compositions may contain water and other solvents as carriers. Primary or secondary low molecular weight alcohols such as methanol, ethanol, propanol and isopropanol are suitable. Monohydroxy alcohols are preferred for solubilizing the surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxyl groups (e.g., propylene glycol, ethylene glycol, glycerin and 1,2-propanediol) may also be used.

The detergent compositions of the invention will preferably be formulated such that during use in aqueous cleaning processes the wash water will have a pH between about 6.5 and about 11, preferably between about 7.5 and about 10.5. Liquid product formulations preferably have a pH between about 7.5 and about 9.5, more preferably between about 7.5 and about 9.0. Procedures for controlling pH at recommended levels of use include buffering agents, alkali, acids, etc., which are well known to those skilled in the art.

The invention further relates to a method for improving the performance of detergents comprising anionic, nonionic and / or cationic surfactants and an activating additive of zeolite or layered silicate, or a mixture thereof, by incorporating into said composition said amide surfactant based polyhydroxy fatty acid amide such that the weight ratio of zeolite and / or layered silicate to polyhydroxy fatty acid amide surfactant is from about 1:10 to about 20: 1.

The invention further relates to a method of cleaning substrates such as fibers, textiles, hard surfaces, leather, etc. by contacting said substrate with a detergent composition comprising one or more ionic, nonionic or cationic surfactants, an activator of zeolite or layered silicate, or a mixture thereof, and said polyhydroxy fatty acid amide, the weight ratio of said activator to the said polyhydroxy fatty acid amide surfactant is from about 1:10 to about 20: 1, in the presence of a solvent such as water or a water-miscible solvent (e.g., primary or secondary alcohols). Stirring is preferably carried out to facilitate cleaning. Suitable mixing means include mixing hands or with cleaning agents such as brushes, fabrics, sponges, rags, etc., automatic dishwashers, automatic washing machines for cleaning textiles (e.g., garments), etc..

In said methods, the preferred weight ratio of the activating additive of zeolite and / or layered silicate to polyhydroxy fatty acid amide is from about 1: 5 to about 15: 1, most preferably from about 1: 3 to about 10: 1.

DETAILED DESCRIPTION OF THE INVENTION

Examples 1-12

This experiment provides an example of a process for the preparation of an N-methyl-1,1-deoxyglucityl lauramide surfactant for use in the invention. Although a skilled chemist may vary the configuration of the device, one suitable device for the application comprises a three-liter four-necked flask equipped with a motor-driven paddle stirrer and a thermometer of sufficient length to contact the reaction medium. The other two flasks are equipped with a nitrogen inlet and a wide-pass side arm (note that a wide-pass side arm is important in the event of a very rapid nitrogen leak) to which an efficient collector condenser and a vacuum outlet are connected. This is connected to the escape of nitrogen and vacuum, and then to the hood and trap. The 500-watt heating jacket with a variable temperature control unit (Variac) used to heat the reaction is placed on the laboratory vise so that it can be easily lifted and lowered to further control the reaction temperature.

N-methylglucamine (195 g, 1.0 mole, Aldrich, M4700-0) and methyl laurate (Procter & Gambia CE 1270, 220.9 g, 1.0 mole) were placed in a flask. The mixture of solid and liquid is heated under stirring under a stream of nitrogen to form a melt (approximately 25 minutes). When the melt temperature reached 145 ° C, a catalyst (anhydrous powdered sodium carbonate, 10.5 g, 0.1 mol, J. T. Baker) was added. The nitrogen inlet is closed and the aspirator and the nitrogen leakage are aligned to create a vacuum of 16.65 kPa. From this point, the reaction temperature is maintained at 150 ° C by aligning the Variac and / or raising or lowering the jacket.

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Within 7 minutes, the first bubbles of methanol are visible on the meniscus of the reaction mixture. This is followed by an intense reaction. Methanol is distilled until its flow rate drops. The vacuum is adjusted to a vacuum of 33.33 kPa. This vacuum is increased approximately as follows (in kPa in minutes): 33.33 kPa in 3 min, 66.66 kPa in 7 min, 83.31 kPa in 10 min. 11 minutes from the start of the methanol evolution, heating and stirring are discontinued, while some foaming occurs. The product is cooled and solidified.

The following examples are intended to illustrate exemplary compositions of the invention, but are not intended to limit or otherwise define the scope of the invention as defined by the claims.

These examples show high performance granular detergent compositions comprising a polyhydroxy fatty acid amide and activating ingredients of zeolite and / or layered silicate.

Basic granules 1 2 3 4 C14-C15 alkyl sulfate 16.9 10.1 11.5 C14-C15 alkylethoxy (2.25) sulfate 5.6 C 1 -C 6 alkylsulfate 16.9 Linear C 2 alkylbenzene sulfonate 10.1 N-methyl N-1-deoxyglucityl- coconut fat amide 5.6 2.4 5.6 5.6 Zeolite A 30.1 18.8 18.8 30.1 sodium citrate 8.3 6.3 sodium carbonate 16.9 21.9 21.9 16.9 sodium silicate 5.6 5.6 5.6 5.6 sodium suifate 15.0 15.0 15.1 15.1 sodium polyacrylate (4500 mhm 1.1 1.1 1.1 1.1 polyethylene glycol (800 mhm) 1.1 1.1 1.1 1.1 tallow fatty acid 1.1 1.1 1.1 1.1 brightening änldlo 0.2 0.2 0.2 0.2

Admixture and spraying 1 2 3 4 protease (1.4% of assets, enzyme) 0.9 0.9 0.0 0.9 perfume 0.3 0.3 0.3 0.3 C12-C13 alkyl ethoxylate (6.5 mole) 1.1 1.1 1.1 1.1 Water 3.8 3.9 3.8 3.8 Pretty 100.0 100.0 100.0 100.0

Examples 1-4 are formulations for preferred use of about 1400 parts per million by weight of wash water for temperatures below about 50 ° C. These examples are realized by combining the basic granular components as a suspension and spray drying them to about 4-8% residual moisture. The remaining dry ingredients are mixed in granular or powder form with spray-dried granules in a rotary mixer and liquid additives (non-ionic surfactant and perfume) by spraying

Basic granules 5 6 7 Linear C. 2 alkylbenzenesulfonate 8.6 C 14 -C 16 alkyl sulfate 12.6 ^ 16 ’^ 18 fatty acid 2.2 2.2 zeolite 7.0 7.0 20.4 polyacrylate (4500 mhm) 3.3 3.3 3.5 polyethylene glycol (8000 mhm) 1.3 1.3 1.5 sodium carbonate 10.7 10.7 Sodium suifate 5.0 5.0 5.0 sodium silicate 5.0 5.0 3.0 spits 7.1 7.1 7.9

admixture 5 6 7 zeolite 5.0 5.0 5.0 N-1-metyl.N deoxyglucityt- coconut fat amide 6.4 6.4 3.2 C16 * C18 methyl ester sulphate 19.1 C12-C18 alkyl sulfate 19.1 various (bleach, asset, prfs .. salts, filler salts, etc.) 17.2 17.2 20.4

spray C12-C13 Alkyl Toxylate (6.5 Mole) 2.0 2.0 2.0 Partial 0.5 0.5 0.5 water and various 8.2 8.3 6.4 Pretty 100.0 100.0 100.0

The compositions of Example 5-7 represent summarized formulations prepared by suspending the basic granular ingredients and spray drying to about 5% moisture and admixing additional granular or powdered dry ingredients. The powder is de-dusted by spraying with liquid additives. The product is intended for use at a concentration of about 1050 parts per million, at a washing temperature of less than about 50 ° C.

Basic granules 8 9 W 11 C12 linear alkylbenzene- Sultanate 6.8 C14-C15 alkylisulfate 4.6 7.6 7.6 C12-C18 alkyl sulfate 2.4 2.4 2.4 2.2 C1S-C18 alkylphethoxytite (11 moles) 1.1 1.1 1.1 zeofit 22.0 24.7 21.3 13.0 acrylate / maleman copolymer (60000 mhm) 4.3 5.6 4.3 polyacrylate (4500 mhm) 5.0 water faculties. ingredients 9.4 9.2 10.1 10.2

Admixture hl-methyl, coconut fat N-1-deoxygluctyl amide 7.0 4.0

N-methyl, N-i-deoxyglucftyl '

tallow fatty acid amide 4.0 6.0 sodium citrate 8.0 sodium carbonate 17.5 17.3 17.5 17.0 sodium silicate 3.5 3.0 3.5 3.0 layered silicate 11.0 - bleaching agents salts, etc.) 27.3 24.1 19.4 24.8

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spray perfume silicone fluid 0.4 0.4 0.4 0.5 0.5 0.5 0.5 0.5 Pretty 100.0 100.0 100.0 100.0

The compositions of Examples 8-10 are preferably used at concentrations of about 6,000 parts per million by weight of wash water at temperatures from about 30 ° C to 95 ° C. These compositions are made by suspending the basic granular ingredients and spray drying to about 9% moisture. The remaining dry ingredients are added and mixed in a rotary mixer, followed by spraying the addition of the final liquid ingredients.

Basic granules 12 13 14 Linear C, 2 alkylbenzene- 5.0 5.9 Sultanate N-methyl, Ν-1-deoxyglucityl- lauramide 5.9 C14-C15 alkyl sulfate 5.9 C12-C18 alkyl sulfate 2.5 2.5 2.5 zeolite 23.5 14.0 20.5 polyacrylate (4500 MW) 3.9 3.9 3.9 sodium citrate 6.0 sodium carbonate 12.7 18.0 12.7 water and various additives 8.1 8.2 8.7

Prlmes and spraying________________________

Coconut fat N-methyl, N-1-deoxyglucitylamide 5.9

N-methyl, N-1-deoxyg lucityi

tallow fatty acid amide various (white, activating salts, filler salts attf.) 5.6 37.5 37.9 39.9 Pretty 100.0 100.0 100.0

Examples 12 to 14 show high performance granular detergent compositions of standard density and for wash temperatures between about 30-95 ° C, at concentrations of about 8,000 parts per million by weight of wash water basis. The compositions are prepared by spray drying the basic granular ingredients to about 10-13% moisture, adding additional dry powder ingredients such as bleach, activators and other supplements and spraying with liquid ingredients such as perfume, nonionic agents or suds suppressors in liquid form.

Example 15

The following alternative process for preparing polyhydroxy fatty acid amides is used. Use a reaction mixture consisting of 84.87 g of fatty acid methyl ester (source: Procter & Gambia methyl ester CE1270), 75 g of N-methyl-D-glucamine (source: Aldrich Chemical Company M4700-0), 1.94 g of sodium methoxide ( source: Aldrich Chemical Company 16, 499-2) and 68.51 g of methyl alcohol. The reaction vessel contains a standard backflow arrangement equipped with a drying tube, condenser and stir bar. In this procedure, N-methylglucamine is combined with methanol under stirring under argon and heating begins with good stirring (stirring bar; reflux). After 15-20 minutes, when the solution reached the desired temperature, the ester and the catalyst were added as sodium methoxide.

Samples are taken periodically to monitor the progress of the reaction, but it is noted that the solution is quite clear after 63.5 minutes. The reaction is almost complete at this point. The reaction mixture was refluxed for 4 hours. The product obtained after removal of methanol weighs 156.15 grams. After vacuum drying and purification, an overall yield of purified product is obtained. However, the percentage is not calculated on this basis because regular sampling during the course of the reaction makes the overall percentage yield insignificant. The reaction can be carried out at 80% to 90% reagent concentrations for up to 6 hours to obtain products with extremely low by-product formation.

The following statements are not intended to limit the invention, but merely to further illustrate the additional features of the technology that can be considered by the formulator in the manufacture of a wide variety of detergent compositions of polyhydroxy fatty acid amides used.

It will be readily appreciated that polyhydroxy fatty acid amides, due to their amide bond, are subject to some instability under highly alkaline or highly acidic conditions. Although some degradation may be tolerated, it is preferred that these materials are not exposed to pH values greater than about 11, preferably 10, or even below about 3, for an excessively prolonged time. The pH values of the final product (liquids) are typically 7.0-9.0.

During the production of polyhydroxy fatty acid amides, it will typically be necessary to at least partially neutralize the basic catalyst used to form the anode bond. While any acid may be used for this purpose, the detergent formulator knows that it is simple and expedient to use an acid that provides an anion that is otherwise useful and desirable in the finished detergent composition. For example, for neutralization purposes, the acid may be citric acid and the resulting citrate ion (about 1%) is left with a suspension of about 40% polyhydroxy fatty acid amides for pumping into the later subsequent phases of the overall detergent production. Similarly, acid forms of materials such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartarate / succinate and the like can be used.

The polyhydroxy fatty acid amides derived from the coconut fatty acid alkyl fatty acids (predominantly C18-C14) are more soluble than their alkyl lactic acid counterparts (predominantly C18-C18). As a result, the C12-C14 materials are somewhat easier to formulate in liquid compositions and are more soluble in cold water-containing laundry solutions. However, the C16-C18 materials are also quite useful, especially in circumstances where hot to hot washing water is used. Indeed, the C16-C18 materials may represent better detergent surfactants than their C12-C14 counterparts. Thus, the formulator may proceed on the basis of the requirement to balance the ease of manufacture of the verses, the effectiveness in choosing a particular polyhydroxy fatty acid amide for use in the formulation.

It will also be appreciated that the solubility of polyhydroxy fatty acid amides can be increased by having saturation and / or branching points of the chains in the fatty acid moiety. Thus, materials such as polyhydroxy fatty acid amides derived from oleic and isostearic acids may be more soluble than their n-alkylated counterparts.

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Similarly, the solubility of polyhydroxy fatty acid amides prepared from disaccharides, trisaccharides, etc. usually greater than the solubility of their monosaccharide derived counterparts. Higher solubility can be particularly useful in formulating liquid compositions. In addition, polyhydroxy fatty acid amides in which the polyhydroxylated group is derived from maltose also prove to be particularly well-functioning detergents when used in combination with conventional alkylbenzene sulfonate (LAS) surfactants. While not wishing to be bound by theory, it appears that the combination of LAS with polyhydroxy fatty acid amides derived from higher saccharides such as maltose causes a substantial and unexpected decrease in interfacial tension in the aqueous environment, thereby promoting detergency performance. (Production of maltose-derived polyhydroxy fatty acid amide is described.

Polyhydroxy fatty acid amides can be produced not only from purified sugars, but also from hydroxylated starches, e.g. cereal starch, potato starch or any suitable starch derived from vegetable products containing mono-, di-, etc. a saccharide required by the formulator. This is particularly important from an economic point of view. Thus, high-glucose cereal syrup, high-maltose cereal syrup, etc. may be suitable and economically used. The feedstock for the polyhydroxy fatty acid amide can also be provided by dehydrated hydrolyzed cellulose pulp.

As noted, polyhydroxy fatty acid amides derived from higher carbohydrates such as maltose, lactose, etc. are more soluble than their glucose counterparts. In addition, it appears that more soluble polyhydroxy fatty acid amides can aid solubilization of their more soluble counterparts in varying degrees. Thus, the formulator may choose a raw material containing, for example, a high glucose corn syrup, or select a syrup that contains a small amount of maltose (e.g., 1% or more). The resulting mixture of polyhydroxy fatty acids will generally have more favorable solubility properties over a wider temperature range and concentrations than would be achieved with pure polyhydroxy fatty acid amide derived from glucose. In addition to all the economic advantages of using sugar mixtures rather than pure sugar starting reagents, polyhydroxy fatty acid amides prepared from mixed sugars can provide very substantial advantages with respect to the efficacy and ease of formulation. However, in some cases, some loss of grease removal capacity (dishwashing) may be observed at levels of maltamide fatty acid above about 25% and some foaming loss above about 33% (the percentages given are percentages of maltamide-derived polyhydroxy fatty acid amide v. , a polyhydroxy fatty acid amide derived from glucose in the mixture). This may vary depending on the chain length of the fatty acid moiety. Typically, the formulator choosing the use of such mixtures may consider it preferable to select mixtures of polyhydroxy fatty acid amides that contain ratios of monosaccharides (e.g. glucose) and Di- and higher saccharides e.g. maltoses from about 4: 1 to about 99: 1.

The production of preferred non-cyclized polyhydroxy fatty acid amides from fatty esters and N-alkyl polyols can be carried out in alcoholic solvents at a temperature of about 30 ° C to 90 ° C, preferably about 50 ° C to 80 ° C. It has now been determined that it may be appropriate for a liquid detergent formulator to carry out such procedures in a 1,2-propylene glycol solvent, since the glycol solvent may not necessarily be removed from the reaction product prior to use in the final detergent formulation. Similarly, the formulator may, for example, consider solid, typically granular detergent compositions, to perform such processes at 30 ° C to 90 ° C in solvents that contain ethoxylated alcohols, such as ethoxylated (EO 3-8) C 12 -C 14 alcohols, such as NEODOL 23 RO6.5 (Shell). When such ethoxylates are used, it is preferred that they do not contain substantial amounts of mono-ethoxylated alcohol (determination T).

Although the processes for making polyhydroxy fatty acid amides are not in themselves part of the invention, the formulator may also consider other polyhydroxy fatty acid amide syntheses as described below.

Typically, the reaction to prepare polyhydroxy fatty acid acyclic amides on an industrial scale will comprise two steps. In a first step, an N-alkyl-polyhydroxyamine derivative will be prepared from the desired sugar or sugar mixture by forming an adduct of N-alkylamine and sugar, and then reacted with hydrogen in the presence of a catalyst. In a second step, reacting said polyhydroxyamine, preferably with a fatty ester, to form an amide bond. While a variety of N-alkyl polyhydroxyamines useful in Step 2 of the reaction sequence can be prepared by various procedures described in the prior art, the following process, which uses an economically advantageous sugar syrup as raw material, is preferred. It should be borne in mind that, for best results, the manufacturer should choose syrups which are fairly light in color or preferably totally colorless (water colors).

Example of preparation of N-alkyl polyhydroxyamines from sugar syrup derived from plant sources.

The first step is the formation of the adduct. The following procedure is a standard process in which about 420 g of an approximately 55% glucose solution (cereal syrup - about 231 g of glucose - about 1.28 mol), having a Gardner color of less than 1, is reacted with about 119 g of about 50 g. % aqueous solution of methylamine (59.5 g methylamine - 1.92 mol). The methylamine solution (MMA) is purified and protected with N 2 and cooled to about 10 ° C to 20 ° C. Cereal syrup is added slowly to the MMA solution at the indicated reaction temperature as shown. The Gardner color is measured at the indicated approximate times in minutes.

TAB. 1

As can be deduced from the above data, the Gardner color for the adduct is much worse when the temperature

SK 279651-6 will increase about 30 ° C and about 50 ° C, the time when the Gardner adduct has a value below 7 is only about 30 minutes. For the next reaction and / or hold time, the temperature should not be less than about 20 ° C. The Gardner color should not be less than about 4 to obtain a good glucamine color.

When lower temperatures are used to form an adduct, the time to reach a substantial equilibrium concentration by using higher amine to sugar ratios is shortened. At a molar ratio of 1.5: 1 amine to sugar, equilibrium is reached in about 2 hours at a reaction temperature of about 30 ° C. At a 1.2: 1 molar ratio, under the same conditions, the time is at least about 3 hours. For good color, the combination of amine: sugar ratio, reaction temperature and reaction time is selected to achieve a substantially equilibrium conversion, e.g. more than about 90%, preferably more than about 95%, and even more preferably more than about 99%, based on sugar and colors, of less than about 7, preferably less than about 4, and most preferably less than about 1 for the adduct.

When using said process at a reaction temperature of less than about 20 ° C and cereal syrups with different Gardner colors as indicated, the color of the MMA adduct (after reaching essentially equilibrium in at least about 2 hours) as shown in the table second

TAB. 2

As can be seen from the table, the starting sugar material must be very close to colorless in order to obtain a continuously acceptable adduct. When the sugar has a Gardner color of about 1, then the adduct is sometimes acceptable and sometimes unacceptable. When the Gardner color is above 11, the resulting adduct is unacceptable. The better the initial color of the sugar, the better the color of the adduct.

The second step is a hydrogen reaction wherein said adduct having Gardner color 1 or less is hydrogenated according to the following procedure.

About 539 g of adduct in water and about 23.1 g of Unidet Cytalytyst G49B Ni catalyst are added to a 1 liter autoclave and purified twice with 1.38 MPa H ₂ at a temperature of about 20 ° C. The hydrogen pressure is increased to about 100 psig and the temperature is raised to about 50 ° C. The pressure is then increased to about 11 MPa and the temperature is maintained at about 50-55 ° C for about 3 hours. The product at this point is approximately 95% hydrogenated. The temperature is then raised to about 85 ° C for about 30 minutes and the reaction mixture is decanted and the catalyst is filtered off. After removal of water and evaporation of MMA, the product is approximately 95% of N-methylglucamine as a white powder.

This procedure is repeated with about 23.1 g of Raney nickel catalyst with the following changes. The catalyst is washed three times and the reactor, with the catalyst in the reactor, is purged twice with 13.8 bar H _2, the reactor is pressurized with hydrogen at 11 psi for two hours, the pressure is released at one hour and the reactor is repressurized to 11 psi. The adduct is then pumped into the reactor at a pressure of 20 psi and a temperature of 20 ° C and the reactor is purged with 1 psi H _2, etc., as above.

In any case, the resulting product is greater than about 95% N-methylglucamine, has less than about 10 parts Ni per million based on glucamine, and has a solution color having a lower Gardner color value than about 2.

Crude N-methylglucamine is color-stable to about 140 ° C for short time exposure.

It is important to have a good adduct having a low sugar content (less than about 50, preferably less than about 1%) and a good color (less than about 7, preferably about 4 Gardner, and most preferably less than about 1).

In another reaction, the adduct is prepared by mixing with about 159 g of about 50% methylamine in water, which is purified and protected with N ₂ at a temperature of about 10-20 ° C. About 330 g of approximately 70% cereal syrup (near white water color) is degassed with N ₂ at a temperature of about 50 ° C and added slowly to the methylamine solution at a temperature less than about 20 ° C. The solution is stirred for about 30 minutes to give approximately 95% adduct as a very light yellow solution.

About 190 g of adduct in water and about 9 g of United Catalytyst G49B Ni catalyst are added to a 200 ml autoclave and purified three times with H ₂ at a temperature of about 50 ° C. The pressure is raised to 1.72 MPa and the temperature is maintained at about 50 ° C to 55 ° C for about 3 hours. The product, which is approximately 95% hydrogenated at this point, is then brought to an elevated temperature of about 85 ° C for about 30 minutes and the resulting product is approximately 95% of N-methylglucamine as a white powder after removal of water and evaporation.

It is also important to minimize contact between adduct and catalyst when the H ₂ pressure is less than about 6.88 MPa to minimize the nickel content of the glucamine. The nickel content of the N-methyl glucamine in this reaction is about 100 parts per million compared to less than 110 parts per million in the previous reaction.

The following reactions with hydrogen are performed to directly compare the effects of reaction temperatures

A 200 milliliter autoclave reactor is used, following a procedure similar to that described above, to obtain the adduct and to carry out the reaction with hydrogen at different temperatures.

The adduct for use in the manufacture of glucamine is prepared by combining approximately 420 g of an approximately 55% solution (231 g of glucose, 1.28 moles) of glucose (cereal syrup), formed using 99DE cereal syrup supplied by CarGill, the solution having a color of less than 1 Gardner and about 119 g of 50% methylamine (59.5 g MMA; 1.92 moles) (from Air Products).

The reaction procedure is as follows:

1. Add about 119 g of a 50% methylamine solution to a nitrogen-protected, nitrogen-protected reactor and cool to less than about 10 ° C.

2. Degass and purify a 55% cereal syrup solution at 10 ° C - 20 ° C with nitrogen to remove oxygen from the solution.

3. Slowly add the corn syrup solution to the methylamine solution and maintain the temperature at less than about 20 ° C.

4. Once all the cereal syrup solution is added, stir for about 1-2 hours.

The adduct is used for the hydrogenation reaction immediately after its formation or stored at a low temperature to prevent further degradation.

The reactions of the glucamine adduct with hydrogen are as follows:

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1. Add about 134 g adduct (less than about Gardner 1) and about 5.8 g G49B Ni to a 200 mL autoclave.

2. Purify the reaction mixture with about 1.38 MPa Efy twice at about 20 ° C - 30 ° C.

3. Pressurize H 2 to about 400 psig and raise the temperature to about 50 ° C.

4. Increase the pressure to approximately 3.45 MPa, allow to react for approximately 3 hours. The temperature is maintained at about 50 ° C - 55 ° C. Sample 1.

5. Raise the temperature to about 85 ° C for about 30 minutes.

6. Decant and filter the nickel catalyst. A sample of 2 shall be taken.

The conditions for constant temperature reactions are as follows:

1. Add about 134 g adduct and about 5.8 g G49B Ni to a 200 mL autoclave.

2. Purify the reaction mixture at about 50 psi H2 twice at low temperature.

3. Pressurize H 2 to about 400 psig and raise the temperature to about 50 ° C.

4. Increase the pressure to approximately 3.45 MPa, allow to react for approximately 3.5 hours. The temperature is maintained at the temperature indicated.

5. Decant and filter the nickel catalyst. Sample 3 is taken for a temperature of about 50 ° C - 55 ° C, Sample 4 for a temperature of about 75 ° C and Sample 5 for a temperature of about 85 ° C (reaction time for about 85 ° C is about 45 minutes).

All experiments yielded a similar purity of N-methylglucamine (about 95%), with Gardner colors in the experiments similar immediately after the reaction, but only a two-stage heat treatment provides good color fastness. The 85 ° C experiment gives a marginal color immediately after the reaction.

Example 16

The preparation of tallow fatty acid amide (solidified) from N-methyl malateamine for use in the detergent compositions of the invention is carried out as follows.

In the first step, maltose monohydrate (Aldrich, 01318KW), methylamine (40 wt% in water) (Aldrich, 03325TM) and Raney nickel as a 50% slurry / UAS 52-73D, Aldrich, 12921LW were used as reactants. ).

The reactants were added to a glass cartridge (250 maltose, 428 methylamine solution, 100 g catalyst slurry - 50 g Raney nickel) and placed in a 3 L swinging autoclave, which was purged with nitrogen (3 x 2 2,78 MPa) and hydrogen (2 x 2.72 MPa) and vibrate under H2 at room temperature over the weekend in the temperature range of 28 ° C to 50 ° C. The crude reaction mixture was vacuum filtered 2X through a microfibrous filter with a silica gel plug. The filtrate is concentrated to a viscous material. The final traces of water are azetropically removed by dissolving the material in methanol and then removing the methanol and water on the rotary launcher. Final drying is carried out under high vacuum. The crude product was dissolved in reflective methanol, filtered, cooled for recrystallization, filtered, and the filtered cake was dried under vacuum at 35 ° C. This is Fraction # 1. The filtrate was concentrated until a precipitate began to form and stored in a refrigerator overnight. The solid was filtered and dried under vacuum. This is Fraction # 2. The filtrate is again concentrated to half its volume and recrystallization is performed. Very little precipitate is formed. A small amount of ethanol is added and the solution is left in the freezer over the weekend. The solid was filtered and dried under vacuum. The combined solids form N-methyl maltamine which is used in step 2 of the overall synthesis.

In the second step, N-methylmaltamine from step 1, stiffened tallow fatty acid methyl esters, sodium methoxide (25% methanol), anhydrous methanol (solvent) are used as reactants, wherein the molar ratio of amine to ester is 1: 1; 10 mol% (w / w of maltamine) and increased to 20 mol% and the solvent content is 50 wt. %.

In a sealed bottle, 20.36 g of tallow methyl ester is heated to its melting point (in a water bath) and filled into a 250 ml three-necked round-bottomed reaction flask with mechanical stirring. The flask is heated to approximately 70 ° C to prevent the ester from solidifying. Separately, 25.0 g of N-methyl maltamine is combined with 45.36 g of methanol and the resulting suspension is added to the tallow ester with good stirring. 1.51 g of 25% sodium methoxide in methanol is added. After four hours, the reaction mixture did not become clear, so an additional 10 mol% catalyst (to a total of 20 mol%) was added and the reaction was allowed to continue overnight at about 68 ° C, after which time the mixture became clear. The flask is then adjusted for distillation. The temperature was raised to 110 ° C. Distillation at atmospheric pressure is continued for 60 minutes. The distillation is then started under high vacuum and continued for 114 minutes. The product is left in the reaction flask at 110 ° C (outside temperature) for 60 minutes. The product was taken from the flask and triturated in ethyl ether over the weekend. The ether is removed on a rotary evaporator and the product is stored overnight in an oven and ground to a powder. Any residual N-methyl maltamine is removed from the product using silica gel. The silica gel suspension in 100% methanol is filled into a funnel and washed several times with 100% methanol. A concentrated sample of the product (20 g in 100 mL of 100% methanol) was poured onto silica gel and eluted several times under vacuum and several methanol washes. The collected eluent was evaporated to dryness in a rotary evaporator. Any residual tallow ester was removed by trituration in ethyl acetate overnight followed by filtration. The product is an N-methylmaltamine alkylated tallow fatty acid.

In an alternative process, step 1 of the previous reaction process may be carried out using a commercially available cereal syrup containing glucose or glucose mixtures and typically 5% or more maltose. The resulting polyhydroxy fatty acid amides and mixtures thereof can be used in the detergent compositions of the invention.

In yet another process, step 2 of the previous reaction process can be carried out in 1,2-propylene glycol or NEODOLE. At the discretion of the formulator, propylene glycol or NEODOL need not be removed from the reaction product prior to its use for formulating detergent compositions. Again, at the desire of the formulator, the methoxide catalyst may be neutralized with citric acid to obtain sodium citrate, which may remain in the polyhydroxy fatty acid amide.

Depending on the desire of the formulator, the compositions discussed herein may comprise more or less different suds control agents. Typically, high sudsing is desirable for dishwashing, so no suds control agent is required. For the washing of fabrics in top-load washing machines, some suds control may be desirable and, in front-load washing machines, a great deal of suds control may be preferred. A wide variety of suds control agents are known in the art and can be routinely selected here as desired. Indeed, the choice of suds control agents or suds control agents for any particular detergent composition will depend not only on the presence and amount of polyhydroxy fatty acid amide used therein, but also on the other surfactants present in the formulation. However, it appears that silicone-based suds control agents of different types (i.e. can be used in smaller amounts) are more effective for use with polyhydroxy fatty acid amides than various other types of suds control agents. Silicone suds control agents available as X2-3419 and 02-3302 (Dow Coming) are particularly useful herein.

The fabric wash composition formulator, which may advantageously comprise a soil release agent, has a choice of a variety of known materials (see, for example, U.S. Patent Nos. 3,952,152, 4,116,885, 4,238,531, 4,702,857,4,721,580, and 4,877,896). Other soil release materials that can be used include the nonionic oligomeric esterification product of the reaction mixture comprising a source of C 1 -C 4 alkoxy-terminated polyethoxy units (e.g. CH 3 [OCH 2 CH 2] 169 H), a terephthaloyl unit source (e.g. dimethyl terephthalate); a source of poly (oxyethylene) oxy units (e.g., polyethylene glycol 1500); a source of oxyisopropyleneoxy units (e.g., 1,2-propylene glycol) ·, and a source of oxyethyleneoxy units (e.g., ethylene glycol), particularly where the molar ratio of oxyethyleneoxy units to oxyisopropyleneoxy units is at least about 0.5: 1. Such anionic soil release agents. have the general formula:

ô o n

- O-R · fCHjCHiOlx, wherein R ¹ is a lower (e.g. C 1 -C 4) alkyl, especially methyl; x and y are integers from 6 to about 100; m is an integer from about 0.75 to about 30; n is an integer from about 0.25 to about 20 and R ² is a mixture of both H and CH 3 to provide a molar ratio of oxyethylene: oxyisopropyleneoxy of at least about 0.5: 1.

Another suitable type of soil release agent useful in the compositions of the invention is of the generally anionic type disclosed in U.S. Pat. No. 4,877,896, but provided such agents are substantially free of HOROH-type monomers wherein R is propylene or higher alkyl. The soil release agents of U.S. Pat. No. 4,877,896 may thus contain, for example, the reaction product of dimethyl terephthalate, ethylene glycol, 1,2-propylene glycol and 3-sodium sulfobenzoic acid, while these additional soil release agents may contain, for example, the reaction product of dimethyl ether terephthalate, ethylene glycol, 5-sodium sulfobisophthalate and 3-sodium sulfobisophthalate. Such agents are preferred for use in granular laundry detergents.

The formulator may also determine that it is preferable to include a non-borate bleach, especially in high performance granules

IU0- (CH _t CM) x

washing detergents. There is a variety of peroxide bleaches available on the market and usable here, but among them is suitable and economical percarbonate. Thus, the compositions of the invention may comprise a solid percarbonate bleach, normally in the form of the sodium salt, comprised in an amount of from 3% to 20% by weight, more preferably from 5% to 18% by weight and most preferably from 9% to 15% by weight of the composition.

Sodium percarbonate is an addition compound having the formula corresponding to 2Na2CO3.3H2CO2 and is commercially available as a crystalline solid. Most commercially available materials include a small amount of a heavy metal scavenger such as EDTA, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) or aminophosphinate incorporated during the manufacturing process. For use in the invention, the percarbonate can be incorporated into the detergent compositions without additional protection, but preferred embodiments of the invention use a stable form of material (FMC). Although a variety of coatings may be used, sodium silicate with a ratio of SiO 2: Na 2 O of 1.6: 1 to 2.8: 1, preferably 2.0: 1, applied as an aqueous solution and dried to provide a content level of 2 % to 10% (normally from 3% to 5%) of solid silicate particles based on the weight of percarbonate. Magnesium silicate and a chelating agent may also be used so that one of these may also be included in the coating.

The particle size range of crystalline percarbonate is from 350 microns to 450 microns with a center of approximately 400 microns. When coated, these particles have a size in the range of 400 to 600 microns.

Although the heavy metals present in the sodium carbonate used for the production of percarbonate can be controlled by the inclusion of scavengers in the reaction mixture, the percarbonate nevertheless requires protection from the heavy metals present as impurities in the other components of the product. It has been found that the total content of iron, copper and manganese ions in the product should not exceed 25 parts per million and preferably should be less than 20 parts per million to avoid an unacceptably negative effect on the percarbonate stability. The modern thickened laundry granules have the following composition.

Example 17

The components of wt. %

C1-4-C1-5 alkyl alcohol sulfonic acid13.0

C14-C15 alkylpolyethoxy (2.25) sulfonic acid 5.6

C 12 -C 13 alkyl polyethoxylate (6.5) 1.45

C12-C114 fatty acid N-methylglucamide 2.5 sodium aluminosilicate (as hydrated

Zeolite A) 25.2 crystalline layered silicate-based 23.2 citric acid 10.0 sodium carbonate active ingredient to yield. pH at wash 9.90 Sodium polyacrylate (MW 2000 - 4500) 3.2 Diethylenetriamine pentaacetic acid 0.45

Savinase ² 0.70 6-Nonanoylamino-6-oxo-peroxycaproic acid 7.40 Sodium perborate monohydrate 2.10 Nonanoylbenzenesulfonic acid 5.00 Brightening agent 0.10

SK 279651Β6

Layer silicate based activators are known in the art. Most preferred are layered sodium silicates. See e.g. layer silicate activators according to U.S. Pat. No. 4,664,895, issued May 12, 1987, which is incorporated herein by reference.

^ Available from Novo Nordisk A / S, Copenhagen.

Significantly most preferred granules of said types are those containing from about 0.0001% to about 2% by weight of said polyhydroxy fatty acid amide, and most preferably wherein the anionic surfactant is not an alkylbenzenesulfonate surfactant.

Example 18

The following example illustrates a detergent composition of the invention with a perborate bleach plus a bleach activator, which is prepared by mixing said ingredients in a mixing drum.

In the example, Zeolite A refers to a hydrated crystalline Zeolite A containing about 20% water and having an average particle size of 1 to 10, preferably 3 to 5 microns; LAS stands for C12.3 linear sodium alkyl benzene sulphate; AS is sodium C14-C15 alkyl sulfate; nonionic agent means coconut alcohol alcohol concentrated with about 6,5 moles of ethylene oxide per mole of alcohol and free of unethoxylated and monoethoxylated alcohol, also abbreviated as CnAE6.5T; and DTPA means diethylenetriamine pentacetate.

Weight parts

Final composition % granules Basic aranula ¹ 51.97 100.00 AS 9.44 18.16 LAS 2.92 5.62 humidity 4.47 8.60 sodium silicate (1.6 ratio) 1.35 2.60 sodium sulphate 6.47 12.45 sodium polyacrylate (4500 mol. 2.61 5.02 PEG 8000 1.18 2.27 nonionic agent 0.43 0.59 sodium carbonate 13.29 25.57 brightener 0.20 0.38 sodium aluminosilicate 9.11 17.53 DTPA 0.27 0.52 perfume 0.20 0,38 Granulv NAPAA ² 6.09 100.00 NAPM 2.86 46,96 LAS 0.30 4.93 sulfate and various 2.93 48.11 NOBS ^ granules 3.88 100.00 NOBS 3.15 81.19 LAS 0.12 3.09 PEG 8000 0.19 4.90 Differently 0.42 10.82 Zeolite aranulv 12,00 100.00 sodium aluminosilicate 7.39 61.58 PEF8000 1.50 12.58 nonionic Reagent 1.16 9.70 humidity 1.68 13.83 Differently 0.29 2.42

admixture stratified sodium silicate SKS-6 15.84 protease (0.078 mg / g activity) 0.52 perborate monohydrate sodium 1.33 citric acid 6.79 C12-C114 N-methylglucamide 1.58 Total final composition

The base granules are produced by spray drying from an aqueous mixture of the above ingredients by stirring with a crutcher.

2-A freshly prepared sample of NAPAA is obtained in the form of a wet cake which typically consists of about 60% water, about 2% oxygen available from peracid (AvO) (corresponding to about 36% NAPAA) and the remainder (about 4%) unreacted starting material. This wet cake is a crude reaction product of NAAA (adipic acid monononylamide), sulfuric acid and hydrogen peroxide, which is subsequently quenched by addition to water followed by filtration, washed with distilled water, washed with phosphate buffer and finally subjected to suction filtration to obtain a wet cake . A portion of the wet cake is air dried at room temperature to obtain a dry sample, which typically consists of about 5% AvO (corresponding to about 90% NAPAA) and about 110% unreacted starting material. When dry, the pH of the sample is about 4.5. The granules are prepared by mixing 51.7 parts dry NAPAA wet cake (containing about 10% unreacted ingredients), about 11.1 parts paste (45% active) of C12.3 linear sodium alkylbenzene sulfonate (LAS), about 43.3 parts sodium sulfate, and about 30 parts of water in the CUISINART mixer. After drying, the granules (which contain about 47% NAPAA) are sized by passing through a No. 1 sieve. 14 Tyler mesh and retain any particles that do not pass through sieve no. 65 Tyler Mesh The average peracid amide particle is about 5 to 40 microns, and the mean particle size is about 10-20 microns, as determined by Malvem particle size analysis.

NOBS (nonanoyloxybenzenesulfonate) granules are prepared according to U.S. Pat. No. 4,997,596 issued

5, 3, 1991, which is incorporated herein by reference.

⁴ Zeolite granules having the following composition are made by mixing Zeolite A with PEG 8000 and CnAE6.5T in an Eirich energy intensive mixer R08.

Weight diets

Before drying assessments Zeolite A (includes bind, water) 70.00 78.90 PEG 8000 10.80 12.49 CnAE6.5T 8.40 9.72 Free water 10.80 0.80

PEG 8000 is in aqueous form containing 50% water and is at a temperature of about 12.8 ° C. CnAE6.5T is in a liquid state and is maintained at a temperature of approximately 32.2 ° C. Both liquids are combined by pumping through a 12-element static mixer. The resulting binder material has an exit temperature of about 23.9 ° C and a viscosity of about 5000 c / s. The ratio of PEG 8000 and CnAE6.5T passing through the static mixer is 72: 28.

SK 279651-6

The Eirich Energy Intensive Mixer R08 is operated in batch type mode. First, weigh 34.1 kg of powdered Zeoäte A into the pan of the mixer. The mixer is started by first allowing the pan to rotate counter-clockwise at approximately 75 rpm and then allowing the rotor blade to rotate clockwise at 1800 rpm. The binder material is then pumped from the static mixer directly into the Eirich energy mixer R08 containing Zeolite A. The binder feed rate is about 2 minutes. The mixer continues stirring for a further one minute for a total batch time of approximately 3 minutes. The batch is then discharged and collected in a fiber drum.

The batch step is repeated until approximately 225 kg of wet product has accumulated. This discharged product is then dried in a fluidized bed at 116 ° C - 132 ° C. The drying process removes most of the free water amen! a composition as described. All the energy input to the product is at a batch mode of about 1362 Nm / kg at a rate of about 2.26 N / kg-s.

Example 19

The granular laundry detergent composition suitable for use at the relatively high concentrations common to pre-load automatic washing machines, particularly in Europe and over a wide temperature range, is as follows.

Component of masses. %

SOKALAN CP5 (100% active as Na sof) 13.52

DEQUEST 2066 (100% as acid) 20.46

TINOPALDMS ^{1 * 3 4} 0.28

MgSO ₄ 0.49

Zeolite A (anhydrous 2 · 5 / u) 17.92

CMC (100 active) * 0.47

Νβ2 <Χ> 39,44 citric acid3,5 layered silicate SKS-612,9 tallow alkyl sulphate (100% active; per salt) 2,82 ^c 14- ^c 15 alkyl sulphate (100% active; per salt) 3,5 ^C 12- C15 alkyl EO (3) sulphate1,76 θ1β-ω8 N-methylglucamide4,1

DOBANOL C12-C15 EO (3) 3.54

LIPOLASE (100,000 LU / g)

SAVINASE (4.0 KNPU) 61.65 perfume 0.53

X2-3419? 0,22 starch1,08 stearyl alcohol0,35 penetri sodium acetate (coated) 22,3 tevaacetylenediamine (TAED) 5,9 phthalocyanine zinc0,02 water (except zeolite) residue

SOKALAN is sodium polyacrylate / sodium maleate available from Co. Hoechst.

Pentaphosphonomethyl diethylenetriamine of the type manufactured by Monsanto.

Optical brightener available from Ciba Geigy.

Available from Metasaliton under circulation. name. Finnfix. LIPOLASE is a lipolytic enzyme from NOV O. ^ SAVINASE is a protease enzyme from NOVO.

⁷ X2-3419 is a silicone suds suppressor available from Dow Coming.

The granule preparation process comprises various tower drying processes (A), agglomeration (B), addition of dry ingredients (C), etc., as indicated. The percentages are based on the finished composition.

First, using standard procedures, the following ingredients are mixed with a crutcher and dried in a drying tower (A).

SOKALAN CP5 3,52%

DEQUEST 2066 0.45%

TINOPAL DMS 0,28% magnesium sulphate 0,49%

ZEOLITE A 7,10%

CMC 0,47%

Further, the agglomeration of the surfactants (B) is carried out. The agglomeration (BI) of the tallow alkyl sulfate salt and the C12-C15 EO (3) sullite paste sodium salt is first carried out. 50% active tallow alkyl sulfate paste and 70% C12-C15 EO (3) sulfate paste are agglomerated with Zeolite A and sodium carbonate according to the following recipe (contribution to detergent formulation after agglomerate drying).

tallow alkylsultät 2,82%

C12-C15 EO (3) sulphate 1.18%

Zeolite A 5.3% sodium carbonate 4.5%

Then (B2) C14-C15 alkyl sulfate, C12-C15 alkyl ethoxysulfate, DOBANOL C10-C18 EO (3) and C18-C18 n-methylglucamide are agglomerated. The Cg-Cg glucamide material is combined with DOBANOL C12-C15 EO (3) present during the reaction with methyl ester and N-methylglucamine. C12-C15EO (3) acts as a melting point reducing agent, allowing the reaction to proceed without the formation of cyclic glucamides, which are undesirable. A mixture of 20% DOBANOL C12-C15 EO (3) and 80% C16-C18 N-methylglucamide is obtained and agglomerated together with 19% sodium carbonate.

Said particle is then agglomerated with an active paste (70%) of the sodium salt of C1q-10g alkyl sulfate and C12C15EO (3) sulfate and ZEOLITE A and sodium carbonate added. The particles exhibit good dispersibility C ₆ -Ci8 N-methyl cold water.

The overall composition of these particles (contribution to the formulation)

detergent after drying the agglomerate) is: C16-C18 N-methylglucamide 4.1% DOBANOL C12-C15 EO 0,94% Sodium carbonate 4.94% Zeolite A 5.3% At C14-C115 alkylsultat 3.5% Na C ₁₂ -C 15 EO (3) sulfate 0.59% The next step is the formulation dry ingredients The following ingredients are added: percarbonate 22.3% TAED (tetraacetylenediamine) 5.9% SKS 6 layered silicate from Hoechst 12,90% citric acid 3.5% lipolase 0.42% SAVINASE 4.0 KNPU 100,000 LU / g 1,65% Zinc phthalocyanide (photobleach) 0.02%

SK 279651-6

In addition, the following ingredients are applied by spraying (D) DOBANOL C12-C115 EO (3) 2.60% perfume 0.53%

The (E) silicone suds suppressor Z2-3419 (95% -97% linear silicone with a high relative weight of 3-5% hydrophobic silica) from Dow Coming with Zeolite A (size 2-5 / u) is agglomerated together as suds suppressors. , starch and stearyl alcohol binder. This particle has the following composition:

Zeolite A 0,22% starch 1,08%

X2-3419 0.22% stearyl alcohol 0.35%

The detergent composition is characterized by excellent solubility, higher efficacy and excellent foaming control when used in a European washing machine, e.g. when using 85 g of detergent in an AEG-type washing machine for washing cycles at 30 ° C, 40 ° C, 60 ° C and 90 ° C.

Example 20

In any of the preceding examples, the fatty acid glucamide surfactant may be replaced by an equivalent amount of maltamide surfactant, or mixtures of glucamide and maltamide surfactants derived from plant sources. The compositions have shown that the use of ethanolamides helps the stability of the finished formulations at lower temperatures. In addition, the use of aminoxyde and / or sulfobetaine (aka sultain) surfactants provides for better foaming.

When particularly high foaming compositions are desired, it is preferred that less than about 5%, more preferably less than about 2%, and most preferably substantially no C 12 or higher fatty acids are present, as these may suppress foaming. Thus, the high suds composition formulator avoids the use of a number of such suds suppressing fatty acids in compositions with polyhydroxy fatty acid amides and / or prevents the formation of C 14 higher fatty acids when storing the finished compositions. One simple composition is to use C ester reactants to prepare polyhydroxy fatty acid amides for the compositions of the invention. The use of aminoxyd or sulfobetaine surfactants can overcome some of the negative effects on foaming caused by fatty acids.

A formulator wishing to add anionic optical brighteners to liquid detergents containing relatively high concentrations (e.g., 10% or more) of anionic or polyanionic substituents such as polycarboxylate builders may find it useful to premix the brightener with water and polyhydroxy fatty amide amide. and then adding the premix to the final composition.

Dispersants in the form of polyglutamic acid and polyaspartic acid can advantageously be used with zeolite-activated detergents. Other examples of useful suds control additives are AE fluid or flakes and DC-544 (Dow Coming).

It will be appreciated by those skilled in the art of chemistry that the preparation of polyhydroxy fatty acid amides for compositions of the invention using di- and higher carbohydrates such as maltose will result in the formation of polyhydroxy fatty acid amides wherein the linear substituent Z is terminated with polyhydroxyl circular structure. Such materials are considered to be fully applicable and do not depart from the scope and spirit of the invention described and explained in the description and defined in the claims.

Claims (10)

An activated detergent composition comprising a single or multi-ionic, non-ionic or cationic detersive surfactant, or mixtures thereof, optionally detersive ingredients and optionally auxiliary builders, comprising at least 1 wt. % of a detergent builder of zeolite or layered silicate, or a mixture thereof, and at least 1 wt. % of the amide material in the form of a polyhydroxy fatty acid amide of the formula O Rl II I R2-C-N-Z, wherein R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R2 is a C5-C31 hydrocarbon group, Z is a linear hydrocarbon group substituted by at least 3 hydroxyl groups directly attached to the hydrocarbon group or an alkoxylated derivative thereof. 2. A detergent composition according to claim 1, wherein the zeolite builder is zeolite A. The composition of claim 1, wherein the Z moiety in the amide material in the form of a polyhydroxy fatty acid amide is derived from a reducing sugar, R 1 is methyl, and R 2 is C 9 -C 17 alkyl or alkenyl. The composition of claim 3, wherein Z comprises -CF 12 (CHOH) 4 CH 2 OH. The composition of claim 1, wherein the Z moiety in said polyhydroxy fatty acid amide is derived from maltose. 6. The composition of claim 1 wherein the Z moiety in said polyhydroxy fatty acid amide is derived from a mixture of monosaccharides, disaccharides, and optionally higher carbohydrates, wherein the mixture comprises at least 1 wt. % of at least one disaccharide, preferably maltose. The detergent composition of claim 1, wherein the ratio of zeolite: polyhydroxy fatty acid amide is from 1: 10 to 20: 1, preferably 1: 5 to 15: 1, most preferably 1: 3 to 10. : first 8. A detergent composition according to claim 1 comprising one or more anionic surfactants selected from the group consisting of alkyl sulfates, alkylethoxylated sulfates, alkyl ester sulfonates, preferably methyl ester sulfonates, and alkyl benzene sulfonates. 9. A detergent composition according to claim 8, further comprising an alkyl ethoxylate or alkyl polyglycoside nonionic surfactant, or a mixture thereof. SK 279651Β6 10. A detergent composition according to claim 1, further comprising a polycarboxylate builder.